Agricultural pyridinesulfonamides

ABSTRACT

N-(heterocyclicaminocarbonyl)pyridinesulfonamides; are useful for the regulation of plant growth and as pre-emergence and post-emergence herbicides.

RELATED APPLICATIONS

This application is a continuation-in-part of my copending applicationU.S. Ser. No. 083,753 filed Oct. 23, 1979, now abandoned which is acontinuation-in-part of my copending application U.S. Ser. No. 966,258,filed Dec. 4, 1978, now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to pyridinesulfonamides which are useful asagricultural chemicals.

French Pat. No. 1,468,747 discloses the following para-substitutedphenylsulfonamides, useful as anti-diabetic agents: ##STR1## whereinR=H, halogen, CF₃ or alkyl.

Logemann et al. Chem. Ab., 53, 18052 g (1959), disclose a number ofsulfonamides, including uracil derivatives and those having the formula:##STR2## wherein R is butyl, phenyl or ##STR3## and R₁ is hydrogen ormethyl. When tested for hypoglycemic effect in rats (oral doses of 25mg/100 g), the compounds in which R is butyl and phenyl were mostpotent.

Wojciechowski, J. Acta. Polon. Pharm. 19, p. 125-5 (1962) [Chem. Ab., 591633 e] describes the synthesis ofN-[(2,6-dimethoxypyrimidin-4-yl)aminocarbonyl]-4-methylbenzenesulfonamide:##STR4## Based upon similarity to a known compound, the author predictedhypoglycemic activity for the foregoing compound.

Netherlands Pat. No. 121,788, published Sept. 15, 1966, teaches thepreparation of compounds of Formula (i), and their use as general orselective herbicides, ##STR5## wherein

R₁ and R₂ may independently be alkyl of 1-4 carbon atoms; and

R₃ and R₄ may independently be hydrogen, chlorine or alkyl of 1-4 carbonatoms.

Compounds of Formula (ii), and their use as antidiabetic agents, arereported in J. Drug. Res. 6, 123 (1974). ##STR6## wherein R is pyridyl.

In U.S. Ser. No. 029,821, herbicidal compounds such asN-heterocyclic-N'(arylsulfonyl)carbamimidothioates (or compounds whereina thienyl radical is substituted for the aryl radical), such as methylN'-(2-chlorophenylsulfonyl)-N-(4-methoxy-6-methylpyrimidin-2-yl)carbamimidothioateare taught.

United States Pat. No. 3,689,549 F (Sept. 5, 1972) to R. P. Williamsdiscloses "heterocyclic sulfonamides wherein the heteroatoms are inertcan be used, e.g., compounds having the furan, thiophene or pyridinenucleus," in the production of sulfonyl isocyanates from sulfonamides ina sulfolane solvent.

B. G. Boggiano, V. Petrow, O. Stephenson and A. M. Wild, in Journal ofPharmacy and Pharmacology 13, 567-574 (1961) disclose the followingcompounds which were tested for hypoglycemic activity. ##STR7## is in 2or 3 position.

J. Delarge in Acta Pol. Pharm. 34, 245-249 (1977) disclosesN-alkylcarbamoylpyridinesulfonamides, as described in the structurebelow, as mild antiinflammatory agents and strong diuretics. ##STR8##R=3-, 4-, 5-, 6-Me, 2-, 4-, 6-Cl, 3-Br, 4-ET₂ N, 4-Me₂ CHNH, 4-(3-ClC₆H₄)NH, 4-(3-CF₃ C₆ H₄)NH

R'=Et, Pr, Me₂ CH, Bu ##STR9## in 2, 3 and 4 position.

German Pat. No. 2,516,025 (Nov. 6, 1975) to J. E. Delarge, C. L. Lapiereand A. H. Georges discloses the following compounds as inflammationinhibitors and diuretics. ##STR10##

R=C₆ H₄ R³ (R³ =Cl, CF₃, Me, MeO, H, Br, F, NO₂, Et, NH₂), Et, iso-Pr,4-methylfuryl, C₆ H₃ Cl₂ -, C₆ H₃ (CF₃)Cl;

R'=alkylcarbamoyl, cyclohexylcarbamoyl, arylcarbamoyl, CSNHCH₂ CH═CH₂,CONHC₆ H₄ Cl-p, alkylthiocarbamoyl, H, COEt;

R² =H, Me;

X=NH, NMe, O, S, NEt; and

n=0,1.

United States Pat. No. 3,346,590 (Oct. 10, 1967) (to K. Dickere and E.Kuhle) discloses the following pyridinesulfonyl isothiocyanates as novelcompounds. ##STR11##

The presence of undesired vegetation causes substantial damage to usefulcrops, especially agricultural products that satisfy man's basic foodand fiber needs, such as cotton, rice, corn, wheat, soybean and thelike. The current population explosion and concomitant world food andfiber shortage demand improvements in the efficiency of producing thesecrops. Preventing or minimizing the loss of a portion of such valuablecrops by killing or inhibiting the growth of undesired vegetation is oneway of improving this efficiency.

A wide variety of materials useful for killing or inhibiting(controlling) the growth of undesired vegetation is available; suchmaterials are commonly referred to as herbicides. The need exists,however, for still more effective herbicides that destroy or controlweeds without causing significant damage to useful crops.

SUMMARY OF THE INVENTION

The invention relates to compounds of Formula I and their agriculturallysuitable salts, suitable agricultural compositions containing them andmethods of using them as general and selective pre-emergence andpost-emergence herbicides and as plant growth regulants. ##STR12##

R₁ is H, Cl, Br, F, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio,##STR13##

R₂ is H, Cl, Br or CH₃ ;

R₃ and R₄ are independently H or CH₃ ;

R₅ is C₁ -C₆ alkyl, C₃ -C₆ alkenyl, CH₂ CH₂ OCH₃, CH₂ CH₂ OCH₂ CH₃, CH₂CH₂ CH₂ OCH₃ or CH₂ CH₂ Cl;

R₆ and R₇ are independently CH₃ or CH₃ CH₂, or R₆ and R₇ can be takentogether to form --(CH₂)₄ --, --(CH₂)₅ -- or --CH₂ CH₂ OCH₂ CH₂ --;

R₁₀ and R₁₁ are independently CH₃ or CH₃ CH₂ ;

W is oxygen or sulfur;

X is CH₃, --OCH₃ or --OCH₂ CH₃ ;

Y is H, Cl, CH₃, CF₃, --NHCH₃, --N(CH₃)₂, --CH₂ OR₈, --CH₂ CH₂ OR₈,--OCH₂ CF₃ or VR₉ ;

Z is CH or N;

V is oxygen or sulfur;

R₈ is CH₃ or CH₃ CH₂ ;

R₉ is ##STR14##

Y₁ is H, CH₃ or OCH₃ ; and

X₁ is H, Cl, --OCH₃, --OCH₂ CH₃, or CH₃ ;

and agricultural salts thereof; providing that:

(1) both X₁ and Y₁ are not simultaneously hydrogen;

(2) when R is ##STR15## then R₃ and R₄ are both H; and

(3) R₁ is at the 2- or 4-position of the pyridine ring.

Preferred Compounds

Preferred in order of increasing activity and/or increasingly favorableease of synthesis are:

(1) Compounds of the generic scope wherein R₃ is H and W is oxygen;

(2) Compounds of Preferred (1) wherein R₂ is hydrogen;

(3) Compounds of Preferred (2) wherein R₁ is Cl, CH₃ O or CH₃ ;

(4) Compounds of Preferred (3) which are 2- or 4-chloro-3-pyridylsulfonyl compounds;

(5) Compounds of the generic scope or Preferred (1) (4) wherein##STR16##

(6) Compounds of Preferred (5) wherein R₄ is hydrogen;

(7) Compounds or Preferred (5) wherein R₁ is chlorine;

(8) Compounds of Preferred (5) wherein X is CH₃ or --OCH₃ ; and Y isCH₃, --OCH₃, OCH₂ CH₃ or --CH₂ OCH₃.

More Preferred still for their higher activity and/or more favorableease of synthesis are those compounds of Preferred (8) wherein R₃ and R₄are hydrogen and W is oxygen.

Specifically Preferred compounds are:

(1)2-Chloro-N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl)]-3-pyridinesulfonamide;

(2)2-Chloro-N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-3-pyridinesulfonamide;

(3)2-Chloro-N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-3-pyridinesulfonamide;

(4)2-Chloro-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-3-pyridinesulfonamide;

(5)2-Chloro-N-[(4,6-dimethyl-1,3,5-triazin-2-yl)aminocarbonyl]-3-pyridinesulfonamide;and

(6)2-Chloro-N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-3-pyridinesulfonamide.

Synthesis

The synthesis of pyridinesulfonylisocyanates, the compounds of FormulaIIIA can be carried out by reacting a suitably substitutedN-(alkylaminocarbonyl)pyridinesulfonamide with phosgene in a refluxingsolvent such as xylene or chlorobenzene followed by filtration of thesolution at room temperature and removal of the solvent. This reactionis shown in Equation 1.

Equation 1 ##STR17## wherein R₁ and R₂ are as previously defined.

N-(alkylaminocarbonyl)pyridinesulfonamides of Formula II may beconveniently prepared by the reaction of equimolar amounts of anappropriate pyridinesulfonamide, an alkyl isocyanate and an anhydrousbase such as K₂ CO₃ or CaCO₃ in an anhydrous solvent such as acetone oracetonitrile. Addition of water and adjustment of the pH to about 3 withHCl, followed by filtration yields the desiredN-(alkylaminocarbonyl)pyridinesulfonamides.

Pyridinesulfonylisothiocyanates of Formula IIIB can be preparedaccording to the procedure taught by K. Dickere and E. Kuhle in UnitedStates Pat. No. 3,346,590 (10/10/1967) whereby a suitablepyridinesulfonyliminodithiocarbonate IV is reacted with phosgene in thepresence of a solvent such as toluene or xylene. The procedure isillustrated in Equation 2.

Equation 2 ##STR18## wherein R₁ and R₂ are as previously defined.

Compounds of Formula I are conveniently prepared by reacting anappropriately substituted pyridinesulfonylisocyanate orpyridinesulfonylisothiocyanate of Formula III with an appropriatelysubstituted amino pyrimidine or amino triazine of Formula V, accordingto the procedure of Equation 3.

Equation 3 ##STR19## wherein R, R₁, R₂, R₄ and W are as previouslydefined.

The reaction of Equation 3 is best carried out in inert aprotic organicsolvents such as methylene chloride, tetrahydrofuran or acetonitrile, atambient pressure and temperature. The mode of addition is not critical;however, it is often convenient to add the sulfonyl isocyanate orisothiocyanate to a stirred suspension of amine V. Since suchisocyanates and isothiocyanates are liquids, low melting solids or arereadily soluble in solvents such as those listed above, their additioncan be easily controlled.

The reaction is generally exothermic. In some cases, the desired productis soluble in the warm reaction medium and on cooling crystallizes inpure form. Other products which are soluble in the reaction mixture areisolated by evaporation of the solvent, trituration of the solid residuewith solvents such as 1-chlorobutane or ethyl ether, and filtration.

As shown in Equation 4, compounds of Formula Ia, wherein R₃ is methyland W is O, can be prepared by methylation of salts VI wherein M is analkali metal cation such as sodium (derived from compounds of FormulaIa, wherein R₃ is hydrogen).

Equation 4 ##STR20## X being an incipient anion and n being an integercorresponding to the valence of X.

The reaction of Equation 4 is best carried out in aprotic organicsolvents such as tetrahydrofuran, dimethylformamide, ordimethylacetamide, at ambient temperature. Methylating agents VII, suchas dimethyl sulfate or methyl iodide, can be employed. The desiredproduct can be isolated by pouring the reaction mixture into water andfiltering off the precipitated solid.

As shown in Equation 5, compounds of Formula Ia' wherein R and R₄ are asdefined previously, can also be prepared by the reaction of anappropriately substituted pyridyl sulfonyl-N-methylcarbamyl chloride orsulfonyl-N-methylthiocarbamyl chloride of Formula VIII with anappropriate aminopyrimidine or aminotriazine of Formula V.

Equation 5 ##STR21## wherein R, R₁, R₂, R₄ and W are as previouslydefined.

The preparation of ureas and thioureas, like those of Formula I, fromamines and carbamyl chlorides and thiocarbamyl chlorides is well knownto the art. The reaction can best be carried out by adding equivalentamounts of the chloride VIII and amine V to an inert organic solvent,such as tetrahydrofuran, xylene, or methylene chloride, in the presenceof acid acceptor, such as triethylamine, pyridine, or sodium carbonateemploying temperatures from 20° to 130°. Soluble products can beisolated by filtering off precipitated salts and concentration of thefiltrate. Insoluble products can be filtered off and washed free ofsalts with water.

The chlorides of Formula VIII can be prepared by phosgenation orthiophosgenation of N-alkylsulfonamide metal salts. The sulfonamide saltis added to an excess of phosgene or thiophosgene in an inert organicsolvent, such as tetrahydrofuran, toluene, or xylene, whereupon, afterremoval of the excess phosgene, the chloride VIII can be isolated orreacted in situ with the amine V.

Compounds of Formula I, wherein R and R₄ are defined previously can alsobe prepared by the reaction scheme shown in Equations 6, 7 and 8.

Equation 6 ##STR22##

wherein R₁ and R₂ are as previously defined.

Dialkyl esters of N-(pyridinylsulfonyl)carbonimidothioic acids ofFormula X wherein R₁₂ is C₁ -C₅ alkyl, can be conveniently prepared bythe reaction of an appropriate pyridinesulfonamide, carbon disulfide, analkali metal hydroxide and an alkyl halide in a suitable solvent, suchas dimethylformamide or dimethylsulfoxide at ambient temperature. Goodyields can be obtained if alkali metal hydroxide and carbon disulfideare added in portions to the solution of pyridinesulfonamide, followedby a dropwise addition of the alkyl halide. The reaction is generallyexothermic. The desired product can be isolated by pouring the reactionmixture into cold water and filtering off the precipitated solid.

Equation 7 ##STR23## wherein R, R₁, R₂, R₄ and R₁₂ are as previouslydefined.

The reaction of Equation 7 is best carried out in inert aproticsolvents, such as tetrahydrofuran, N,N-dimethylformamide, ordimethylacetamide at ambient temperature. The anion of theaminopyrimidine or aminotriazine can be prepared by the reaction of analkali metal hydride with an appropriate amine V and a compound ofFormula X is added to the stirred solution of the anion species atambient temperature. Addition of water, followed by filtration, yieldsthe desired solid product.

Pyridinylsulfonylcarbonimidothioic acid esters of Formula XI, asprepared in Equation 7 can be converted to the correspondingN-(pyrimidinyl or triazinyl aminocarbonyl)pyridinesulfonamides accordingto Equation 8.

Equation 8 ##STR24## wherein R, R₁, R₂, R₄ and R₁₂ are as previouslydefined.

The reaction of Equation 8 is best carried out in aqueoustetrahydrofuran, or aqueous acetonitrile. Oxidizing agents, such asmercuric oxide/boron trifluoride etherate, or mercuric chloride/calciumcarbonate may be employed at temperatures of 20° to 130° C. The desiredproduct can be filtered off and washed free of salts with water.

As shown in Equation 9, compounds of Formula Ib, wherein R, R₁, R₂ andR₃ are as previously defined are alternatively prepared by the reactionof an appropriately substituted pyridylsulfonamide with the appropriatetriazine or pyrimidine isothiocyanate of Formula XII.

Equation 9 ##STR25## The reaction of Equation 9 is best carried out bydissolving or suspending the sulfonamide and isothiocyanate in a polarsolvent such as acetone, acetonitrile, ethyl acetate ormethylethylketone, adding an equivalent of a base such as potassiumcarbonate and stirring the mixture at ambient temperature up to thereflux temperature for one to twenty-four hours. In some cases, theproduct precipitates from the reaction mixture and can be removed byfiltration. The product is stirred in dilute mineral acid, filtered andwashed with cold water. If the product does not precipitate from thereaction mixture it can be isolated by evaporation of the solvent,trituration of the residue with dilute mineral acid and filtering offthe insoluble product.

The heterocyclic isothiocyanates which are used in the procedure ofEquation 9 are prepared, for example, according to the method of Japanpatent application Pub: Kokai 51-143686, June 5, 1976, or that of W.Abraham and G. Barnikow, Tetrahedron 29, 691-7 (1973).

N-(Triazinyl or pyrimidinylaminothioxomethyl)pyridinesulfonamideswherein R, R₁, R₂, R₃, and R₄ are as defined previously can be convertedto the corresponding aminocarbonylpyridinesulfonamides as shown inEquation 9A.

Equation 9A ##STR26## The reaction of Equation 9A is best carried out bysuspending the appropriate compound of Formula Ib and mercuric oxide ina solvent such as acetone, acetonitrile or methylethyl ketone andstirring the mixture at ambient temperature for 10 to 72 hours.Filtration to remove the insoluble mercury compound and evaporation ofthe solvent yields a residue containing the desired product.

Compounds of formula I, where R₁ ≠CO₂ R₅, are conveniently prepared byreacting the appropriately substituted pyridinesulfonamide with theappropriate methyl pyrimidinyl carbamate or methyl triazinyl carbamateof Formula XIII in the presence of an equimolar amount oftrimethylaluminum according to the procedure of Equation 10.

Equation 10 ##STR27##

The reaction of Equation 10 is best carried out in methylene chloride at25° to 40° for 24 to 96 hours under a nitrogen atmosphere. The productis isolated by the addition of an aqueous acetic acid solution followedby extraction of the product into methylene chloride or directfiltration of a product of low solubility. The product is purified bytrituration with solvents such as ether or subjected to columnchromatography.

The procedure for the preparation of agriculturally suitable salts ofthe compounds of Formula I is described for alkali metal salts, ammoniumsalts and acid addition salts in Equations 11, 12 and 13 respectively.Preparation of other salts would be obvious to one skilled in the art.

Equation 11 ##STR28## wherein R, R₁, R₂, R₄ and W are as previouslydefined.

The reaction of Equation 11 is best carried out by adding to asuspension of one equivalent of the appropriate pyridinesulfonamide in asolvent such as methanol or ethanol one equivalent of an appropriatebase such as a metal alkoxide, hydroxide, or carbonate in the samesolvent. Following heating at 40°-50° the solvent is removed in vacuo toyield the desired salt which can be triturated with solvents such asethylacetate, ethylether or hexane to give the desired solid alkalimetal salts.

Equation 12 ##STR29## wherein

R₁₃ is C₁ -C₁₂ alkyl, CH₂ CH₂ OH, C₆ H₅ or H

R₁₄ is C₁ -C₁₂ alkyl, CH₂ CH₂ OH, C₆ H₅ or H

R₁₅ is C₁ -C₁₂ alkyl, CH₂ CH₂ OH, C₆ H₅ or H ##STR30## with the provisothat R₁₃, R₁₄ and R₁₅ cannot all be phenyl at the same time.

The ammonium salts of substituted pyridinesulfonamides can be preparedas described in Equation 12.

Generally, one equivalent of an appropriate amine such as ammonia,dimethylamine, diethanolamine or ethanolamine is added neat or in asolvent such as methylene chloride or methanol to a suspension of theappropriate benzenesulfonamide in the same solvent. The solvent isremoved under reduced pressure to yield as product the desired salt.

Equation 13 ##STR31##

As shown in Equation 13, the acid addition salts ofN-(heterocyclicaminocarbonyl)pyridinesulfonamides of Formula X can beprepared by heating at about 40°-50° a suspension of theaminocarbonylpyridinesulfonamide in a solvent such as ethanol or hexanecontaining an equivalent amount of an acid such as HCl, HBr, H₂ SO₄,p-toluenesulfonic acid or trichloroacetic acid. In the case of volatilemineral acids such as HCl or organic acids such as trichloro acetic acidan excess may be employed. Removal of solvent in vacuo yields thedesired salt.

The synthesis of sulfur compounds of pyridine has been reviewed in "TheChemistry of Heterocyclic Compounds", a series published by IntersciencePubl., New York and London. Pyridinesulfonamides are described by H. L.Tale in "Pyridine and Its Derivatives" Supplement, Part 4 (1975) whichis herein incorporated by reference.

Those intermediate sulfonamides of Formula IX not described in theaforementioned reference may be prepared by conventional methods,including nucleophilic displacement of the known 2- and4-halopyridine-3-sulfonamides of Formula XVI. These are illustrated inEquations 14 and 15.

Equation 14

R₁ ═NR₆ R₇, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, F, ##STR32##

Equation 15

R₁ ═CO₂ R₅, ##STR33##

The intermediate pyridinesulfonamides of Formula IX where R₁ is SO₂ NR₁₀R₁₁ may be prepared by the sequence of reactions as shown in Equation16.

Equation 16 ##STR34## wherein R₂, R₁₀ and R₁₁ are as previously definedand X is Cl or Br.

Nucleophic displacement of halogen from 2- or 4-halo-3-nitropyridines ofFormula XVII with benzyl mercaptan affords the 2- or4-benzylthio-3-nitropyridines. Oxidation of benzylic sulfides to thecorresponding sulfonyl chlorides, e.g., XVIII, with chlorine in aqueousacetic acid is taught by R. F. Langler, Canad. J. Chem., 54, 498 (1956).Methods for conversion of sulfonyl chlorides of Formula XVIII tosulfonamides of Formula XIX are well known in the art.

Following reduction by conventional methods of the nitro group ofcompounds of Formula XIX, 3-aminopyridines of Formula XX are convertedto the corresponding 3-pyridinesulfonylchlorides by the method disclosedby H. L. Yale and F. Sowinski, J. Org. Chem., 25, 1824 (1960). Methodsof converting the sulfonyl chlorides to the sulfonamides, such as thoseof Formula IX, are well known to the skilled artisan.

The compounds of this invention and their preparation are furtherillustrated by the following examples wherein temperatures are given indegrees centrigrade.

cl EXAMPLE 1

2-Chloro-3-pyridinesulfonylisocyanate

To 125 ml of dry xylene was added with stirring 20.7 g of2-chloro-N-(butylcarbamoyl)-3-pyridinesulfonamide. This solution washeated to reflux, and phosgene added until no further uptake of this gaswas observed. It was then cooled, filtered and the solvent was removedin vacuo to yield 2-chloro-3-pyridinesulfonylisocyanate as an oil Bp108°-110° (0.7 mm Hg). This product showed a sharp absorption peak inthe infrared region at 2220 cm⁻¹.

By using the procedure of Example 1 with the appropriateN-(alkylcarbamoyl)pyridinesulfonamide, the sulfonyl isocyanate of Table1 can be prepared. The pyridinesulfonylisothiocyanates of Table 1 areprepared according to the method of K. Dickere and E. Kuhle as describedin Equation 2.

                  TABLE I                                                         ______________________________________                                         ##STR35##                                                                    R.sub.1             R.sub.2     W                                             ______________________________________                                        2-CH.sub.3          6-CH.sub.3  S                                             4-CO.sub.2 C.sub.2 H.sub.5                                                                        H           O                                             2-CO.sub.2 CH.sub.3 H           O                                             4-CO.sub.2 (iC.sub.3 H.sub.7)                                                                     H           O                                             4-OCH.sub.3         H           O                                             4-Cl                H           O                                             2-F                 H           O                                             2-Br                H           O                                             4-SC.sub.4 H.sub.9  H           O                                             2-SC.sub.2 H.sub.5  H           O                                             4-Br                H           O                                             4-N(CH.sub.3).sub.2 H           O                                             4-SO.sub.2 N(CH.sub.3).sub.2                                                                      H           O                                             H                   H           O                                             2-CH.sub.3          H           O                                             2- -n-C.sub.4 H.sub.9                                                                             H           O                                             4-CH.sub.2 CH.sub.3 H           S                                             4- .sub.-i-C.sub.3 H.sub.7                                                                        5-Cl        O                                             2-Cl                H           O                                             4-Br                H           S                                             4-F                 H           O                                             2-OCH.sub.3         4-Cl        O                                             4-O( -n-C.sub.3 H.sub.7)                                                                          H           S                                             2-SCH.sub.3         H           O                                             4-SCH.sub.2 CH.sub.3                                                                              2-CH.sub.3  O                                             2-N(CH.sub.3).sub.2 H           O                                             4-N(CH.sub.3)C.sub.2 H.sub.5                                                                      6-CH.sub.3  O                                             2-SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                               H           O                                             4-SO.sub.2 N(CH.sub.3).sub.2                                                                      5-CH.sub.3  O                                             2-CO.sub.2 CH.sub.3 5-Br        O                                             4-CO.sub.2 i-C.sub.3 H.sub.7                                                                      H           S                                             2-Br                6-Br        O                                             4-Cl                2-Cl        O                                             H                   6-CH.sub.3  S                                             4-CH.sub.3          2-Cl        O                                             H                   6-Cl        O                                             4- -n-C.sub.4 H.sub.9                                                                             H           S                                             2-CO.sub.2 .sub.-i-C.sub.3 H.sub.7                                                                H           O                                             2-CO.sub.2 CH.sub.3 H           O                                             H                   H           S                                             2-Cl                H           S                                             2-CO.sub.2 .sub.-i-C.sub.3 H.sub.7                                                                H           S                                             2-CO.sub.2 CH.sub.3 H           S                                             2-CH.sub.3          H           S                                             H                   H           S                                             2-SO.sub.2 N(CH.sub.2 CH.sub.3).sub.2                                                             6-CH.sub.3  O                                             2-N(CH.sub.3)CH.sub.2 CH.sub.3                                                                    6-Cl        O                                             2-N(CH.sub.3).sub.2 6-CH.sub.3  S                                             2-N(CH.sub.2 CH.sub.3).sub.2                                                                      6-Cl        O                                             2-SO.sub.2 N(CH.sub.3)CH.sub.2 CH.sub.3                                                           6-CH.sub.3  O                                             4-SO.sub.2 N(CH.sub.2 CH.sub.3).sub.2                                                             2-CH.sub.3  O                                             ______________________________________                                    

EXAMPLE 2 Methyl(4,6-dimethylpyrimidin-2-yl)carbamate

To 2-Amino-4,6-dimethylpyrimidine (10 g) dissolved in dimethylcarbonate(80 ml) was added sodium methoxide (4.4 g) and the mixture refluxed forfour hours. The mixture was cooled and acetic acid (5 ml) was added. Themixture was then partitioned between water (100 ml) and methylenechloride (300 ml). A second methylene chloride extraction of the aqueousphase was made and the combined methylene chloride phase washed withwater (50 ml) containing NH₄ Cl. The solvent was evaporated and theresidue triturated with a methylene chloride/1-chlorobutane mixture. Thefiltrate, on concentration and addition of hexane gave 6.7 g of the purecarbamate, m.p. 80°-85° C. IR: NH at 3200; carbonyl at 1745 cm⁻¹. NMR:2.4 ppm, 2xCH₃, singlet; ArH 6.75 ppm 1H, singlet 8.9 ppm, NH, braod.

EXAMPLE 3N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-3-pyridinesulfonamide

To a slurry of 3-pyridinesulfonamide (1 m mole) in methylene chloride isadded 2 m mole of trimethylaluminum. Following methane evolution, thereaction mixture becomes homogeneous, whereupon 1 m mole of methyl(4,6-dimethylpyrimidin-2-yl)carbamate is added, and stirring iscontinued for 66 hours. Aqueous acetic acid is added and the product isextracted into methylene chloride. The solvent is evaporated and theproduct is isolated by trituration on chromatography.

EXAMPLE 42-Chloro-N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-3-pyridinesulfonamide

To a stirred suspension of 1.4 g of 2-amino-4-methoxy-6-methylpyrimidinein 20 ml of dry acetonitrile at room temperature was added 2.2 g of2-chloropyridine-3-sulfonylisocyanate. The mixture was stirred forseveral hours and filtered. Evaporation of the filtrate yielded a solidresidue which was stirred in approximately 30 ml of water whileadjusting the pH of this mixture to 11 by the addition of 10% of NaOH.This solution was filtered, the filtrate pH adjusted to pH 7 by adding10% hydrochloric acid and the resulting neutral solution was againfiltered. The desired product was then precipitated from this filtrateby adjusting the pH to 2, collected in a sintered funnel and dried in avacuum oven at room temperature. It melted at 165°-168°.

By using the procedure of Examples 2 and 3 with the appropriatelysubstituted 2-aminopyrimidine and the appropriately substitutedpyridine-3-sulfonamide, or the procedure of Example 4 with an equivalentamount of a 2-aminopyrimidine and appropriately substitutedsulfonylisocyanate or isothiocyanate, the compounds of Table II can beprepared.

                                      TABLE II                                    __________________________________________________________________________     ##STR36##                                                                    R.sub.1      R.sub.2                                                                             R.sub.4                                                                            W   X     Y           m.p.                            __________________________________________________________________________    H            H     H    O   CH.sub.3                                                                            CH.sub.3    152° dec.                H            H     H    S   CH.sub.3                                                                            OCH.sub.3                                   H            H     H    O   OCH.sub.3                                                                           OCH.sub.3   176° dec.                2-Cl         H     H    O   OCH.sub.3                                                                           OCH.sub.3   160-165°                 2-Cl         H     H    O   CH.sub.3                                                                            CH.sub.2 OCH.sub.3                          2-Cl         H     H    O   CH.sub.3                                                                            CH.sub.3    140-145°                 2-Cl         H     H    S   CH.sub.3                                                                            SCH.sub.3                                   2-Cl         H     CH.sub.3                                                                           O   CH.sub.3                                                                            OCH.sub.3                                   2-CH.sub.3   6-CH.sub.3                                                                          H    O   CH.sub.3                                                                            OCH.sub.3                                   4-CH.sub.3   H     CH.sub.3                                                                           O   CH.sub.3                                                                            OCH.sub.2 CH.sub.2 OCH.sub.3                2-nC.sub.3 H.sub.7                                                                         H     H    O   CH.sub.3                                                                            OCH.sub.3                                   4-C.sub.2 H.sub.5                                                                          6-Cl  H    O   CH.sub.3                                                                            OCH(CH.sub.3)CO.sub.2 CH.sub.3              4-Cl         H     H    O   CH.sub.3                                                                            N(CH.sub.3).sub.2                           4-F          H     H    O   CH.sub.3                                                                            OCH.sub.2 CH.sub.2 CO.sub.2 C.sub.2                                           H.sub.5                                     4-Br         H     CH.sub.3                                                                           S   CH.sub.3                                                                            OCH.sub.3                                   2-Cl         6-Cl  H    O   OCH.sub.3                                                                           OCH.sub.3   182-185°                 2-Cl         6-Cl  H    O   CH.sub.3                                                                            OCH.sub.3   180-183°                 4-OCH.sub.3  H     H    O   CH.sub.3                                                                            OCH.sub.3                                   2-OC.sub.2 H.sub.5                                                                         H     H    O   OCH.sub.3                                                                           OCH.sub.3                                   4-S -nC.sub.3 H.sub.7                                                                      H     H    O   CH.sub.3                                                                            CH.sub.3                                    2-SCH.sub.3  H     H    O   OCH.sub.3                                                                           OCH.sub.3                                   4-N(CH.sub.3).sub.2                                                                        H     H    O   CH.sub.3                                                                            CH.sub.3                                    2-N(CH.sub.3).sub.2                                                                        H     H    O   CH.sub.3                                                                            OCH.sub.3                                   2-N(CH.sub.3)C.sub.2 H.sub.5                                                               H     H    O   CH.sub.3                                                                            OCH.sub.3                                   2-SO.sub.2 N(CH.sub.3).sub.2                                                               H     H    O   OCH.sub.3                                                                           CH.sub.2 OCH.sub.3                          4-SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                        H     H    S   CH.sub.3                                                                            CH.sub.3                                    2-CO.sub.2 CH.sub.3                                                                        4-CH.sub.3                                                                          H    O   OCH.sub.3                                                                           OCH.sub.3                                   4-CO.sub.2 iC.sub.3 H.sub.7                                                                H     CH.sub.3                                                                           O   CH.sub. 3                                                                           OCH.sub.3                                   2-CO.sub.2  -nC.sub.4 H.sub.9                                                              6-CH.sub.3                                                                          H    O   CH.sub.3                                                                            CH.sub.3                                    4-CO.sub.2 C.sub.2 H.sub.5                                                                 H     H    O   OCH.sub.3                                                                           OCH.sub.3                                   4-CO.sub.2 CH.sub.3                                                                        5-Br  H    O   CH.sub.3                                                                            OCH.sub.3                                   H            6-Cl  H    O   OCH.sub.3                                                                           OCH.sub.3   211-14°                  2-SO.sub.2 N(CH.sub.2 CH.sub.3).sub.2                                                      H     H    O   OCH.sub.3                                                                           OCH.sub.3                                   2-N(CH.sub.3)CH.sub.2 CH.sub.3                                                             6-Cl  H    O   CH.sub.3                                                                            CH.sub.3                                    2-N(CH.sub.3)CH.sub.2 CH.sub.3                                                             6-Cl  H    O   CH.sub.3                                                                            OCH.sub.3                                   2-N(CH.sub.3)CH.sub.2 CH.sub.3                                                             6-Cl  H    O   OCH.sub.3                                                                           OCH.sub.3                                   2-N(CH.sub.3).sub.2                                                                        6-CH.sub.3                                                                          H    S   CH.sub.3                                                                            CH.sub.3                                    2-N(CH.sub.3).sub.2                                                                        6-CH.sub.3                                                                          H    S   CH.sub.3                                                                            OCH.sub.3                                   2-N(CH.sub.3).sub.2                                                                        6-CH.sub.3                                                                          H    S   OCH.sub.3                                                                           OCH.sub.3                                   2-N(CH.sub.2 CH.sub.3).sub.2                                                               H     H    O   CH.sub.3                                                                            CH.sub.3                                    2-N(CH.sub.2 CH.sub.3).sub.2                                                               6-Cl  H    O   CH.sub.3                                                                            OCH.sub.3                                   2-N(CH.sub.2 CH.sub.3).sub.2                                                               6-Cl  H    O   OCH.sub.3                                                                           OCH.sub.3                                   2-SO.sub.2 N(CH.sub.3)CH.sub.2 CH.sub.3                                                    6-CH.sub.3                                                                          H    O   CH.sub.3                                                                            CH.sub.3                                    2-SO.sub.2 N(CH.sub. 3)CH.sub.2 CH.sub.3                                                   H     H    O   CH.sub.3                                                                            OCH.sub.3                                   2-SO.sub.2 N(CH.sub.3)CH.sub.2 CH.sub.3                                                    6-CH.sub.3                                                                          H    O   OCH.sub.3                                                                           OCH.sub.3                                   4-SO.sub.2 N(CH.sub.2 CH.sub.3).sub.2                                                      H     H    O   CH.sub.3                                                                            CH.sub.3                                    4-SO.sub.2 N(CH.sub.2 CH.sub.3).sub.2                                                      H     H    O   CH.sub.3                                                                            OCH.sub.3                                   4-SO.sub.2 N(CH.sub.2 CH.sub.3)                                                            H     H    O   OCH.sub.3                                                                           OCH.sub.3                                   __________________________________________________________________________

EXAMPLE 52-Chloro-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-3-pyridinesulfonamide

To a stirred suspension of 1.4 g of 2-amino-4-methoxy-6-methyltriazinein 20 ml of dry acetonitrile at room temperature was added 2.2 g of2-chloropyridine-3-sulfonylisocyanate. The mixture was stirred forseveral hours and then evaporated to dryness. The residue was mixed with30 ml of water and enough 10% sodium hydroxide to adjust the pH to 11.This mixture was filtered and the filtrate adjusted to pH7 by theaddition of 10% hydrochloric acid and then refiltered. Acidification ofthis filtrate to pH2 caused the desired compound to precipitate. Thedesired compound was filtered off and after drying in a vacuum oven wasfound to melt at 160°-165°.

EXAMPLE 6N-[(4,6-Dimethoxy-1,3,5-triazin-2-yl)aminothioxomethyl]-3-pyridinesulfonamide

A mixture of 1.58 g of 3-pyridinesulfonamide, 2.04 g of4,6-dimethoxy-2-isothiocyanato-1,3-5-triazine and 1.5 g of anhydrouspotassium carbonate was stirred in 75 ml of acetone for 60 hours atambient temperature. The reaction mixture was then poured into 500 ml ofcold water, acidified with hydrochloric acid and the precipitatedproduct was removed by filtration to yield 2.7 g of the desiredcompound, m.p. 158°-160°.

EXAMPLE 7N-[(4,6-Dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-3-pyridinesulfonamide

A mixture containing 2.7 g ofN-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminothioxomethyl]-3-pyridinesulfonamide,2.98 g of mercuric oxide and 75 ml of acetone was stirred at ambienttemperature for 60 hours and then filtered. Evaporation of the filtratein vacuo yielded the desired product as a residual white solid of m.p.182°-185° dec.

By using the procedure of Examples 2 and 3, or by using the procedure ofExample 5 with an equivalent amount of a 2-amino-1,3,5-triazine andappropriately substituted sulfonylisocyanate or isothiocyanate, thecompounds of Table III can be prepared. Alternatively,N-(aminothioxomethyl)pyridinesulfonamides of Table III can be preparedaccording to the method of Example 4 by substituting equivalent amountsof an appropriately substituted pyridinesulfonamide andisothiocyanato-1,3,5-triazine. The aminothioxomethylsulfonamidesobtained by the method of Example 6 or by Equations 3 or 5 wherein W=Scan also be converted to the N-(aminocarbonyl)pyridinesulfonamides ofTable III by reaction with mercuric oxide according to the procedure ofExample 7.

                                      TABLE III                                   __________________________________________________________________________     ##STR37##                                                                    R.sub.1     R.sub.2                                                                           R.sub.4                                                                          W X   Y          m.p.                                      __________________________________________________________________________    2-Cl        H   H  S CH.sub.3                                                                          SCH.sub.3                                            2-Cl        H   CH.sub.3                                                                         O CH.sub.3                                                                          OCH.sub.3                                            2-CH.sub.3  6-CH.sub.3                                                                        H  O CH.sub.3                                                                          OCH.sub.3                                            4-CH.sub.3  H   CH.sub.3                                                                         O CH.sub.3                                                                          OCH.sub.2 CH.sub.2 OCH.sub.3                         2-Cl        H   CH.sub.3                                                                         O OCH.sub.3                                                                         OCH.sub.3  115-122°                           2-CO.sub.2 CH.sub.2 CH.sub.2 Cl                                                           H   H  O CH.sub.3                                                                          OCH.sub.3                                            2-CO.sub.2 CH.sub.2CHCH.sub.2                                                             H   H  O CH.sub.3                                                                          OCH.sub.3                                            2-CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                    H   H  O OCH.sub.3                                                                         OCH.sub.3                                            2-CH.sub.3  H   CH.sub.3                                                                         O CH.sub.3                                                                          OCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                2-CH.sub.3  H   H  O CH.sub.3                                                                          OCH.sub.2 CO.sub.2 CH.sub.3                          4-C.sub.2 H.sub.5                                                                         2-CH.sub.3                                                                        H  O CH.sub.3                                                                          OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                   4-n-C.sub.4 H.sub.9                                                                       2-CH.sub.3                                                                        H  S CH.sub.3                                                                          OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                4-Br        5-Cl                                                                              H  O CH.sub.3                                                                          SCH.sub.2 CO.sub.2 CH.sub.3                          2-CO.sub.2 CH.sub.3                                                                       H   H  O CH.sub.3                                                                          S(CH.sub.2).sub.2 CO.sub.2 C.sub.2 H.sub.5           4-CO.sub.2 C.sub.2 H.sub.5                                                                H   H  O OCH.sub.3                                                                         OCH.sub.3                                            4-CO.sub.2i-C.sub.3 H.sub.7                                                               H   CH.sub.3                                                                         S CH.sub.3                                                                          OCH.sub.3                                            6-CO.sub.2 CH.sub.3                                                                       H   H  O CH.sub.3                                                                          OCH.sub.3                                            4-OCH.sub.3 H   H  O CH.sub.3                                                                          OCH.sub.3                                            2-OCH.sub.3 H   H  O OC.sub.2 H.sub.5                                                                  OCH.sub.3                                            4-CH.sub.3  6-Cl                                                                              H  O CH.sub.3                                                                          CF.sub.3                                             4-Cl        H   H  O CH.sub.3                                                                          N(CH.sub.3).sub.2                                    2-F         H   H  S CH.sub.3                                                                          Cl                                                   2-Br        H   H  O CH.sub.3                                                                          Cl                                                   4-OC.sub.2 H.sub.5                                                                        H   H  O CH.sub.3                                                                          SC.sub.2 H.sub.5                                     4-SC.sub.2 H.sub.5                                                                        H   CH.sub. 3                                                                        S CH.sub.3                                                                          S(CH.sub.2).sub.2 OC.sub.2 H.sub.5                   4-SnC.sub.4 H.sub.9                                                                       H   H  O OCH.sub.3                                                                         OCH.sub.3                                            2-SC.sub.2 H.sub.5                                                                        H   H  O CH.sub.3                                                                          OCH.sub.3                                            4-F         H   H  O CH.sub.3                                                                          OCH.sub.2 CH.sub.2 CO.sub.2 C.sub.2 H.sub.5          4-Br        H   CH.sub.3                                                                         S CH.sub.3                                                                          OCH.sub.3                                            2-SCH.sub.3 H   H  O CH.sub.3                                                                          OCH.sub.3                                            Br          H   H  O OCH.sub.3                                                                         OCH.sub.3                                            4-n-C.sub.4 H.sub.9                                                                       H   H  S CH.sub.3                                                                          SCH.sub.2 CO.sub.2 CH.sub.3                          4-n-C.sub.4 H.sub.9                                                                       H   H  O OCH.sub.3                                                                         OCH.sub.3                                            4-F         6-Cl                                                                              H  O OC.sub.2 H.sub.5                                                                  CH.sub.2 OCH.sub.3                                   2-Cl        6-Cl                                                                              H  S OCH.sub.3                                                                         OCH.sub.3  143-145°                           2-Cl        6-Cl                                                                              H  O CH.sub.3                                                                          OCH.sub.3  93-96°                             2-Cl        6-Cl                                                                              H  O OCH.sub.3                                                                         OCH.sub.3  172-177°                           H           H   H  O CH.sub.3                                                                          CH.sub.3                                             H           H   H  S CH.sub.3                                                                          OCH.sub.3                                            H           H   H  O OCH.sub.3                                                                         OCH.sub.3  230° dec.                          2-Cl        H   H  O OCH.sub.3                                                                         OCH.sub.3  144-150°                           2-Cl        H   H  O CH.sub.3                                                                          CH.sub.2 OCH.sub.3                                   2-Cl        H   H  O CH.sub.3                                                                          CH.sub.3   155-158°                           2-CO.sub.2 CH.sub.3                                                                       H   H  O OCH.sub.3                                                                         OCH                                                  2-CO.sub.2 CH.sub.3                                                                       H   H  O CH.sub.3                                                                          OCH.sub.3                                            2-CO.sub.2 CH.sub.3                                                                       H   H  O CH.sub.3                                                                          CH.sub.3                                             2-CO.sub.2i-C.sub.3 H.sub.7                                                               H   H  O CH.sub.3                                                                          CH.sub.3                                             2-CO.sub.2i-C.sub.3 H.sub.7                                                               H   H  O CH.sub.3                                                                          OCH.sub.3                                            2-CO.sub.2i-C.sub.3 H.sub.7                                                               H   H  O OCH.sub.3                                                                         OCH.sub.3                                            4-CH.sub.3  H   H  S CH.sub.3                                                                          OCH.sub.3                                            4-CH.sub.3  H   H  O CH.sub.3                                                                          CH.sub.3                                             4-CH.sub.3  H   H  O OCH.sub.3                                                                         OCH.sub.3                                            2-CH.sub.3  H   H  O OCH.sub.3                                                                         OCH.sub.3                                            2-CH.sub.3  H   H  O CH.sub.3                                                                          OCH.sub.3                                            2-CH.sub.3  H   H  O CH.sub.3                                                                          CH.sub.3                                             4-Cl        H   H  O CH.sub.3                                                                          CH.sub.3                                             4-Cl        H   H  S CH.sub.3                                                                          OCH.sub.3                                            4-Cl        H   H  O OCH.sub.3                                                                         OCH.sub.3                                            4-CO.sub.2 CH.sub.3                                                                       H   H  O CH.sub.3                                                                          CH.sub.3                                             4-CO.sub.2 CH.sub.3                                                                       H   H  O CH.sub.3                                                                          OCH.sub.3                                            4-CO.sub.2 CH.sub.3                                                                       H   H  O OCH.sub.3                                                                         OCH.sub.3                                            4-CO.sub.2i-C.sub.3 H.sub.7                                                               H   H  O CH.sub.3                                                                          CH.sub.3                                             4-CO.sub.2i-C.sub.3 H.sub.7                                                               H   H  O OCH.sub.3                                                                         OCH.sub.3                                            4-CO.sub.2i-C.sub.3 H.sub.7                                                               H   H  O CH.sub.3                                                                          OCH.sub.3                                            4-N(CH.sub.3).sub.2                                                                       H   H  O CH.sub.3                                                                          CH.sub.3                                             4-N(CH.sub.3).sub.2                                                                       H   H  O CH.sub.3                                                                          OCH.sub.3                                            4-N(CH.sub.3).sub.2                                                                       H   H  O OCH.sub.3                                                                         OCH.sub.3                                            4-SO.sub.2 N(CH.sub.3).sub.2                                                              H   H  O CH.sub.3                                                                          CH.sub.3                                             4-SO.sub.2 N(CH.sub.3).sub.2                                                              H   H  O CH.sub.3                                                                          OCH.sub.3                                            4-SO.sub.2 N(CH.sub.3).sub.2                                                              H   H  O OCH.sub.3                                                                         OCH.sub.3                                            2-SO.sub.2 N(CH.sub.2 CH.sub.3).sub.2                                                     H   H  O CH.sub.3                                                                          CH.sub.3                                             2-SO.sub.2 N(CH.sub.2 CH.sub.3).sub.2                                                     H   H  O CH.sub.3                                                                          OCH.sub.3                                            __________________________________________________________________________

By using the procedure of Examples 4 or 5 with an equivalent amount of a3-amino-1,2,4-triazine and appropriately substituted sulfonylisocyanateor isothiocyanate, the compounds of Table IV can be prepared.

                  TABLE IV                                                        ______________________________________                                         ##STR38##                                                                    R.sub.1      R.sub.2  W      Y.sub.1                                                                              X.sub.1                                   ______________________________________                                        2-Cl         H        O      CH.sub.3                                                                             OCH.sub.3                                 2-Cl         H        O      CH.sub.3                                                                             OCH.sub.3                                 2-Cl         H        S      OCH.sub.3                                                                            OCH.sub.3                                 4-C.sub.2 H.sub.5                                                                          2-CH.sub.3                                                                             O      CH.sub.3                                                                             CH.sub.3                                  4-Br         6-Cl     O      CH.sub.3                                                                             OCH.sub.3                                 4-CO.sub.2 C.sub.2 H.sub.5                                                                 H        O      CH.sub.3                                                                             CH.sub.3                                  2-CO.sub.2 CH.sub.3                                                                        H        O      CH.sub.3                                                                             CH.sub.3                                  2-OCH.sub.3  H        O      CH.sub.3                                                                             CH.sub.3                                  2-F          H        S      CH.sub.3                                                                             CH.sub.3                                  2-Br         H        O      OCH.sub.3                                                                            OCH.sub.3                                 6-SC.sub.2 H.sub.5                                                                         H        S      OCH.sub.3                                                                            CH.sub.3                                  4-F          H        S      OCH.sub.3                                                                            CH.sub.3                                  2-Cl         H        O      H      CH.sub.3                                  2-Cl         H        O      CH.sub.3                                                                             OCH.sub. 2 CH.sub.2                       2-N(CH.sub.3).sub.2                                                                        H        O      CH.sub.3                                                                             OCH.sub.3                                 4-SO.sub.2 N(CH.sub.3).sub.2                                                               H        O      OCH.sub.3                                                                            OCH.sub.3                                 ______________________________________                                    

By using the procedure of Examples 4 or 5 with an equivalent amount ofthe appropriate 4-aminopyrimidines and appropriately substitutedsulfonylisocyanate or isothiocyanate, the compounds of Table V can beprepared.

                  TABLE V                                                         ______________________________________                                         ##STR39##                                                                    R.sub.1       R.sub.2  W     Y.sub.1                                                                              X.sub.1                                   ______________________________________                                        2-C.sub.2 H.sub.5                                                                           H        O     OCH.sub.3                                                                            OCH.sub.3                                 4-n-C.sub.4 H.sub.9                                                                         H        S     OCH.sub.3                                                                            CH.sub.3                                  4-F           H        O     OCH.sub.3                                                                            C.sub.2 H.sub.5                           4-SC.sub.2 H.sub.5                                                                          H        S     OCH.sub.3                                                                            OCH.sub.3                                 2-Br          H        O     CH.sub.3                                                                             Cl                                        4-F           H        O     CH.sub.3                                                                             OCH.sub.2 CH.sub.3                        2-OCH.sub.3   H        O     OCH.sub.3                                                                            H                                         2-CO.sub.2 CH.sub.3                                                                         H        O     OCH.sub.3                                                                            OCH.sub.2 CH.sub.3                        2-SO.sub.2 NCH.sub.2 CH.sub.3                                                               H        O     CH.sub.3                                                                             CH.sub.3                                  2-N(CH.sub.3).sub.2                                                                         6-CH.sub.3                                                                             O     OCH.sub.3                                                                            OCH.sub.3                                 4-CO.sub.2 CH.sub.3                                                                         H        O     OCH.sub.3                                                                            Cl                                        4-CO.sub.2 C.sub.2 H.sub.5                                                                  H        O     OCH.sub.3                                                                            OCH.sub. 3                                2-Br          6-Cl     S     OCH.sub.3                                                                            H                                         4-C.sub.2 H.sub.5                                                                           2-CH.sub.3                                                                             O     OCH.sub.3                                                                            Cl                                        2-Cl          H        O     OCH.sub.3                                                                            OC.sub.2 H.sub.5                          2-Cl          H        O     OCH.sub.3                                                                            CH.sub.3                                  2-Cl          H        S     OCH.sub.3                                                                            Cl                                        ______________________________________                                    

By using an appropriate N-[(triazinyl)aminocarbonyl]pyridinesulfonamideor N[(pyrimidinyl)aminocarbonyl]pyridinesulfonamide, the compounds ofFormula I (where R₃ =CH₃) set forth in Table VI can be prepared. Forexample, the compound of Example 4 can be converted toN-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-chloro-N-methyl-3-pyridinesulfonamideby the methylation reaction set forth in Equation 3 as follows: Anequivalent amount of sodium hydride (50% mineral oil dispersion) can beadded to a solution of the compound of Example 4 in dimethylformamideunder a nitrogen atmosphere. After hydrogen evolution has ceased, anequivalent amount of dimethylsulfate can be added. The resultingreaction mixture can be stirred for 2-18 hours and the reaction mixturecan then be poured into a large volume of water to form a precipitatewhich can be filtered to yield the aboveidentified product.

                  TABLE VI                                                        ______________________________________                                         ##STR40##                                                                    R.sub.1    R.sub.2 R.sub.4                                                                              W     X     Y     Z                                 ______________________________________                                        2-Cl       H       H      OCH.sub.3                                                                           OCH.sub.3 CH                                  2-Cl       H       H      CH.sub.3                                                                            OCH.sub.3 N                                   2-Cl       H       CH.sub.3                                                                             CH.sub.3                                                                            OCH.sub.3 CH                                  2-Cl       H       H      CH.sub.3                                                                            OCH.sub.3 CH                                  2-CO.sub.2 CH.sub.3                                                                      H       H      CH.sub.3                                                                            N(CH.sub.3).sub.2                                                                       CH                                  2-CO.sub.2 CH.sub.3                                                                      H       H      CH.sub.3                                                                            N(CH.sub.3).sub.2                                                                       N                                   2-CO.sub.2 C.sub.2 H.sub.5                                                               H       H      CH.sub.3                                                                            OCH.sub.2 CH.sub.2 OCH.sub.3                                                            CH                                  4-COn-C.sub.4 H.sub.9                                                                    H       CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 OCH.sub.3                                                                      N                                   4-CH.sub.3 6-Cl    H      CH.sub.3                                                                            N(CH.sub.3).sub.2                                                                       N                                   4-CH.sub.3 6-Cl    CH.sub. 3                                                                            CH.sub.3                                                                            SC.sub.2 H.sub.5                                                                        CH                                  2-CH.sub.3 6-Cl    H      CH.sub.3                                                                            OCH.sub.3 N                                   2-Br       H       H      CH.sub.3                                                                            OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                                                      CH                                  2-SO.sub.2 NH(CH.sub.3)CH.sub.2 CH.sub.3                                               6-CH.sub.3                                                                          H      OCH.sub.3                                                                             OCH.sub.3 CH                                    4-SO.sub.2 N(CH.sub.2 CH.sub.3).sub.2                                                     H      H      CH.sub.3                                                                            OCH.sub.3 N                                   2-N(CH.sub.2 CH.sub.3).sub.2                                                             6-Cl    H      CH.sub.3                                                                            CH.sub.3  CH                                  4-N(CH.sub.3).sub.2                                                                      H       H      CH.sub.3                                                                            OCH.sub.3 N                                   2-F        6-Cl    H      CH.sub.3                                                                            CF.sub.3  CH                                  4-F        6-Cl    H      CH.sub.3                                                                            OC.sub.2 H.sub.5                                                                        N                                   ______________________________________                                    

EXAMPLE 8 N-(3-Pyridinylsulfonyl)carbonimidodithioic acid, dimethylester

To a stirred solution of 15.8 g of pyridine-3-sulfonamide in 70 ml ofN,N-dimethylformamide was added 6.6 g of powdered potassium hydroxide.The mixture was stirred for 50 minutes at room temperature and 3 ml ofcarbon disulfide was added dropwise. The solution was then stirred atroom temperature for 0.5 hr., then 3.3 g of powdered potassium hydroxideand 1.5 ml of carbon disulfide was added. The mixture was stirred for0.5 hr., then 3.3 g of powdered potassium hydroxide and 1.5 ml of carbondisulfide was added. The mixture was stirred for 0.5 hr. again, andcooled at 0°-5° C., then 13 ml of iodomethane was added dropwise. Theresulting mixture was stirred overnight and poured onto 250 g ofice-water. The precipitate was filtered and rinsed with water untilneutral, then dried at reduced pressure to give 17 g of pale yellowsolid, m.p. 115°-118° C.

Using the method described in Example 8, the compounds of Table VII canbe prepared from the appropriately substituted pyridinesulfonamide andthe appropriate alkylating agent.

                  TABLE VII                                                       ______________________________________                                         ##STR41##                                                                    R.sub.1         R.sub.2   R.sub.12                                            ______________________________________                                        2-Cl            H         CH.sub.3                                            2-CH.sub.3      6-CH.sub.3                                                                              CH.sub.3                                            2-CH.sub.3      H         CH.sub.3                                            4-CH.sub.3      H         CH.sub.3                                            4-C.sub.2 H.sub.5                                                                             2-CH.sub.3                                                                              CH.sub.3                                            4- -n-C.sub.4 H.sub.9                                                                         2-CH.sub.3                                                                              CH.sub.3                                            2-Cl            6-Cl      CH.sub.3                                            4-CO.sub.2 C.sub.2 H.sub.5                                                                    H         CH.sub.3                                            2-CO.sub.2i-C.sub.3 H.sub.7                                                                   H         CH.sub.3                                            4-OCH.sub.3     H         CH.sub.3                                            2- -n-C.sub.4 H.sub.9                                                                         H         CH.sub.3                                            4-CH.sub.3      6-Cl      CH.sub.2 CH.sub.2 CH.sub.3                          4-Cl            H         CH.sub.3                                            2-F             H         CH.sub.3                                            4-Br            H         CH.sub.3                                            4-SC.sub.2 H.sub.5                                                                            H         CH.sub.3                                            2-SC.sub.4 H.sub.9                                                                            H         CH.sub.3                                            2-SC.sub.2 H.sub.5                                                                            H         CH.sub.3                                            4-F             H         CH.sub.3                                            4-Br            H         CH.sub.3                                            2-SCH.sub.3     H         CH.sub.3                                            2-Br            H         CH(CH.sub.3).sub.2                                  4- -n-C.sub.4 H.sub.9                                                                         H         CH.sub.3                                            6- -n-C.sub.4 H.sub.9                                                                         H         CH.sub.3                                            4-F             6-Cl      CH.sub.3                                            H               H         CH.sub.2 CH.sub.2 CH.sub.3                          2-Cl            4-Cl      CH.sub.2 CH.sub.2 CH.sub.3                          2-CO.sub.2 -i-C.sub.3 H.sub.7                                                                 H         CH.sub.2 CH.sub.2 CH.sub.3                          2-CO.sub.2 CH.sub.3                                                                           H         CH.sub.2 CH.sub.2 CH.sub.3                          H               H         CH.sub.2 CH.sub.2 CH.sub.3                          2-Cl            H         CH.sub.2 CH.sub.2 CH.sub.3                          2-CO.sub.2i-C.sub.3 H.sub.7                                                                   H         CH.sub.2 CH.sub.2 CH.sub.3                          2-CO.sub.2 CH.sub.3                                                                           H         CH.sub.2 CH.sub.2 CH.sub.3                          2-CH.sub.3      H         CH.sub.2 CH.sub.2 CH.sub.3                          2-CH.sub.3      H         CH.sub.2 CH.sub.2 CH.sub.3                          H               H         CH.sub.2 CH.sub.3                                   H               H         CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                 4-Cl            H         CH.sub.3                                            4-NO.sub.2      H         CH.sub.3                                            4-NO.sub.2      H         CH.sub.3                                            4-CH.sub.3      H         CH.sub.3                                            4-CH.sub.3      H         CH.sub.3                                            4-CO.sub.2 CH.sub.3                                                                           H         CH.sub.3                                            4-CO.sub.2 CH.sub.3                                                                           H         CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                 4-CO.sub.2 -i-C.sub.3 H.sub.7                                                                 H         CH.sub.3                                            4-SO.sub.2 N(CH.sub.2 CH.sub.3).sub.2                                                         2-CH.sub.3                                                                              CH.sub.3                                            2-N(CH.sub.3).sub.2                                                                           6-CH.sub.3                                                                              CH.sub.2 CH.sub.3                                   4-N(CH.sub.3).sub.2                                                                           H         CH.sub.3                                            4-SO.sub.2 N(CH.sub.3).sub.2                                                                  H         CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                 ______________________________________                                    

EXAMPLE 9N-(4-Methoxy-6-methyl-1,3,5-triazin-2-yl)-N'-(3-pyridinylsulfonyl)carbamimidothioicacid, methyl ester

To a suspension of 0.9 g of sodium hydride (50% oil dispersion) in 25 mlof dry N,N-dimethylformamide was added 2.3 g of2-amino-4,6-dimethoxypyrimidine. The resulting yellow suspension wasstirred at room temperature for 3 hrs., then added to 3.95 g of3-pyridinylsulfonylcarbonimidodithioic acid, dimethyl ester. The reddishslurry was stirred at room temperature for 2 hours, poured into 250 g oficewater and filtered to remove 1.6 g of unreacted, carbonimidodithioicacid, dimethyl ester. The filtrate was adjusted to pH 4 by adding 10%hydrochloric acid and the precipitate was filtered off, rinsed withwater until neutral and then dried invacuo to give 2.6 g of the desiredcompound, m.p. 146°-149° C.

By using the procedure of Example 9 with an equivalent amount of anappropriate aminopyrimidine, or aminotriazine and an appropriatelysubstituted pyridinylsulfonylcarbonimidodithioic acid, dialkyl ester,the compounds of Tables VIII, IX, X and XI can be prepared.

                                      TABLE VIII                                  __________________________________________________________________________     ##STR42##                                                                    R.sub.1    R.sub.2                                                                           R.sub.4                                                                          X   Y          R.sub.12                                     __________________________________________________________________________    2-Cl       H   CH.sub.3                                                                         CH.sub.3                                                                          OCH.sub.3  CH.sub.2 CH.sub.2 CH.sub.3                   2-Cl       H   H  CH.sub.3                                                                          OCH.sub.3  CH.sub.3                                     2-CH.sub.3 6-CH.sub.3                                                                        H  CH.sub.3                                                                          OCH.sub.3  CH.sub.3                                     4-CH.sub.3 H   CH.sub.3                                                                         CH.sub.3                                                                          OCH.sub.2 CH.sub.2 OCH.sub.3                                                             CH.sub.3                                     2-CO.sub.2 CH.sub.2 CH.sub.2 Cl                                                          H   H  CH.sub.3                                                                          OCH.sub.3  CH.sub.3                                     2-CO.sub.2 CH.sub.2 CHCH.sub.2                                                           H   H  CH.sub.3                                                                          OCH.sub.3  CH.sub.3                                     2-CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                   H   H  OCH.sub.3                                                                         OCH.sub.3  CH.sub.3                                     2-CH.sub.3 H   CH.sub.3                                                                         CH.sub.3                                                                          OCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                    CH.sub.3                                     2-CH.sub.3 H   H  CH.sub.3                                                                          OCH.sub.2 CO.sub.2 CH.sub.3                                                              CH.sub.3                                     4-C.sub.2 H.sub.5                                                                        2-CH.sub.3                                                                        H  CH.sub.3                                                                          OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                                                       CH.sub.3                                     4-Br       6-Cl                                                                              H  CH.sub.3                                                                          SCH.sub.2 CO.sub.2 CH.sub.3                                                              CH.sub.3                                     2-CO.sub.2 CH.sub.3                                                                      H   H  CH.sub.3                                                                          S(CH.sub.2).sub.2 CO.sub.2 C.sub.2 H.sub.5                                               CH.sub.3                                     4-CO.sub.2 C.sub.2 H.sub.5                                                               H   H  OCH.sub.3                                                                         OCH.sub.3  CH.sub.3                                     2-CO.sub.2 CH.sub.3                                                                      H   H  CH.sub.3                                                                          OCH.sub.3  CH(CH.sub.3).sub.2                           4-OCH.sub.3                                                                              H   H  CH.sub.3                                                                          OCH.sub.3  CH.sub.3                                     2-OCH.sub.3                                                                              H   H  OC.sub.2 H.sub.5                                                                  OCH.sub.3  CH.sub.3                                     4-CH.sub.3 2-Cl                                                                              H  CH.sub.3                                                                          CF.sub.3   CH.sub.3                                     4-Cl       H   H  CH.sub.3                                                                          N(CH.sub.3).sub.2                                                                        CH.sub.3                                     2-Br       H   H  CH.sub.3                                                                          Cl         CH.sub.3                                     2-OC.sub.2 H.sub.5                                                                       H   H  CH.sub.3                                                                          SC.sub.2 H.sub.5                                                                         CH.sub.3                                     4-S -n-C.sub.4 H.sub.9                                                                   H   H  OCH.sub.3                                                                         OCH.sub.3  CH.sub.3                                     2-SC.sub.2 H.sub.5                                                                       H   H  CH.sub.3                                                                          OCH.sub.3  C.sub.4 H.sub.9                              4-F        H   H  CH.sub.3                                                                          OCH.sub. 2 CH.sub.2 CO.sub.2 C.sub.2 H.sub.5                                             CH.sub.3                                     H          H   H  CH.sub.3                                                                          CH.sub.3   CH.sub.22 -H H H OCH.sub.3 OCH.sub.3 CH.s                                     ub.3                                         2-Cl       H   H  OCH.sub.3                                                                         OCH.sub. 3 CH.sub.3                                     2-Cl       H   H  CH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                       CH.sub.3                                     2-Cl       H   H  CH.sub.3                                                                          CH.sub.3   CH.sub.3                                     2-CO.sub.2 CH.sub.3                                                                      H   H  OCH.sub.3                                                                         OCH        CH.sub.3                                     2-CO.sub.2 CH.sub.3                                                                      H   H  CH.sub.3                                                                          OCH.sub.3  CH.sub.3                                     2-CO.sub.2 CH.sub.3                                                                      H   H  CH.sub.3                                                                          CH.sub.3   CH.sub.3                                     2-CO.sub.2 -i-C.sub.3 H.sub.7                                                            H   H  CH.sub.3                                                                          CH.sub.3   CH.sub.3                                     2-CO.sub.2 -i-C.sub.3 H.sub.7                                                            H   H  CH.sub.3                                                                          OCH.sub.3  CH.sub.3                                     2-CO.sub.2 -i-C.sub.3 H.sub.7                                                            H   H  OCH.sub.3                                                                         OCH.sub.3  CH.sub.3                                     2-CH.sub.3 H   H  OCH.sub.3                                                                         OCH.sub.3  CH.sub.3                                     2-CH.sub.3 H   H  CH.sub.3                                                                          OCH.sub.3  CH.sub.3                                     2-CH.sub.3 H   H  CH.sub.3                                                                          CH.sub.3   CH.sub.3                                     4-Cl       H   H  CH.sub.3                                                                          CH.sub.3   CH.sub.3                                     4-Cl       H   H  OCH.sub.3                                                                         OCH.sub.3  CH.sub.3                                     4-CO.sub.2 CH.sub.3                                                                      H   H  CH.sub.3                                                                          CH.sub.3   CH.sub.3                                     4-CO.sub.2 CH.sub.3                                                                      H   H  CH.sub.3                                                                          OCH.sub.3  CH.sub.3                                     4-CO.sub.2 CH.sub.3                                                                      H   H  OCH.sub.3                                                                         OCH.sub.3  CH.sub.3                                     4-CO.sub.2 -i-C.sub.3 H.sub.7                                                            H   H  CH.sub.3                                                                          CH.sub.3   CH.sub.3                                     4-CO.sub.2 -i-C.sub.3 H.sub.7                                                            H   H  OCH.sub.3                                                                         OCH.sub.3  CH.sub.3                                     4-CO.sub.2 -i-C.sub.3 H.sub.7                                                            H   H  CH.sub.3                                                                          OCH.sub.3  CH.sub.3                                     4-CH.sub.3 H   H  CH.sub.3                                                                          CH.sub.3   CH.sub.3                                     4-CH.sub.3 H   H  OCH.sub.3                                                                         OCH.sub.3  CH.sub.2 CH.sub.2 CH.sub.3                   4-N(CH.sub.3).sub.2                                                                      H   H  CH.sub.3                                                                          CH.sub.3   CH.sub.3                                     4-SO.sub.2 N(CH.sub.3).sub.2                                                             H   H  CH.sub.3                                                                          OCH.sub.3  CH.sub.2 CH.sub.3                            2-SO.sub.2 N(CH.sub.2 CH.sub.3)                                                          H   H  OCH.sub.3                                                                         OCH.sub.3  CH.sub.3                                     2-SO.sub.2 N(CH.sub.2)CH.sub.2 CH.sub.3                                                  6-CH.sub.3                                                                        H  CH.sub.3                                                                          OCH.sub.3  CH.sub.3                                     __________________________________________________________________________

                                      TABLE IX                                    __________________________________________________________________________     ##STR43##                                                                    R.sub.1         R.sub.2                                                                           R.sub.4                                                                          X   Y         R.sub.12                                 __________________________________________________________________________    4-C.sub.2 H.sub.5                                                                             H   H  CH.sub.3                                                                          CF.sub.3  CH.sub.3                                 2-Cl            H   CH.sub.3                                                                         CH.sub.3                                                                          OCH.sub.3 CH.sub.3                                 2-CH.sub.3      6-CH.sub.3                                                                        H  CH.sub.3                                                                          OCH.sub.3 CH.sub.3                                 4-CH.sub.3      H   CH.sub.3                                                                         CH.sub.3                                                                          OCH.sub.2 CH.sub.2 OCH.sub.3                                                            CH.sub.3                                 2-CO.sub.2 CH.sub.2 CHCH.sub.2                                                                H   H  CH.sub.3                                                                          OCH.sub.3 CH.sub.3                                 2-CO.sub.2 CHCHCH(CH.sub.2).sub.2 CH.sub.3                                                    H   H  CH.sub.3                                                                          OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.3               2-CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                        H   H  CH.sub.3                                                                          CH.sub.3  CH.sub.3                                 2-CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub. 3                                              H   H  CH.sub.3                                                                          OCH.sub.3 CH.sub.3                                 2-CO.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                               H   H  CH.sub.3                                                                          OCH.sub.3 CH.sub.3                                 2-CO.sub.2 CH.sub.2 CH.sub.2 Cl                                                               H   H  OCH.sub.3                                                                         OCH.sub.3 CH.sub.3                                 2-CO.sub.2 CH.sub.3                                                                           H   H  CH.sub.3                                                                          S(CH.sub.2).sub.2 CO.sub.2 C.sub.2 H.sub.5                                              CH.sub.3                                 4-CO.sub.2 C.sub.2 H.sub.5                                                                    H   H  OCH.sub.3                                                                         OCH.sub.3 CH.sub.3                                 4-OCH.sub.3     H   H  CH.sub.3                                                                          OCH.sub.3 CH.sub.3                                 4-Cl            H   H  CH.sub.3                                                                          N(CH.sub.3).sub.2                                                                       CH.sub.3                                 4-S -n-C.sub.4 H.sub.9                                                                        H   H  OCH.sub.3                                                                         OCH.sub.3 CH.sub.3                                 2-SC.sub.2 H.sub.5                                                                            H   H  CH.sub.3                                                                          OCH.sub.3 CH.sub.3                                 4-F             H   H  CH.sub.3                                                                          OCH.sub.2 CH.sub.2 CO.sub.2 C.sub.2 H.sub.5                                             CH.sub.3                                 2-Cl            4-Cl                                                                              H  OCH.sub.3                                                                         OCH.sub.3 CH.sub.3                                 2-Cl            4-Cl                                                                              H  CH.sub.3                                                                          OCH.sub.3 CH.sub.3                                 H               H   H  CH.sub.3                                                                          CH.sub.3  CH.sub.3                                 H               H   H  OCH.sub.3                                                                         OCH.sub.3 CH.sub.3                                 2-Cl            H   H  OCH.sub.3                                                                         OCH.sub.3 CH.sub.3                                 2-Cl            H   H  CH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                      CH.sub.3                                 2-F             H   H  CH.sub.3                                                                          CH.sub.3  CH.sub.3                                 2-CO.sub.2 CH.sub.3                                                                           H   H  OCH.sub.3                                                                         OCH       CH.sub.3                                 2-CO.sub.2 CH.sub.3                                                                           H   H  CH.sub.3                                                                          OCH.sub.3 CH.sub.3                                 2-CO.sub.2 CH.sub.3                                                                           H   H  CH.sub.3                                                                          CH.sub.3  CH.sub.3                                 2-CO.sub.2 -i-C.sub.3 H.sub.7                                                                 H   H  CH.sub.3                                                                          CH.sub.3  CH.sub.3                                 2-CO.sub.2 -i-C.sub.3 H.sub.7                                                                 H   H  CH.sub.3                                                                          OCH.sub.3 CH.sub.3                                 2-CO.sub.2 -i-C.sub.3 H.sub.7                                                                 H   H  OCH.sub.3                                                                         OCH.sub.3 CH.sub.3                                 2-CH.sub.3      H   H  OCH.sub.3                                                                         OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3      2-CH.sub.3      H   H  CH.sub.3                                                                          OCH.sub.3 CH.sub.3                                 2-CH.sub.3      H   H  CH.sub.3                                                                          CH.sub.3  CH.sub.3                                 4-Cl            H   H  CH.sub.3                                                                          CH.sub.3  CH.sub.3                                 4-Br            H   H  OCH.sub.3                                                                         OCH.sub.3 CH.sub.3                                 4-CO.sub.2 CH.sub.3                                                                           H   H  CH.sub.3                                                                          CH.sub.3  CH.sub.3                                 4-CO.sub.2 CH.sub.3                                                                           H   H  CH.sub.3                                                                          OCH.sub.3 CH.sub.3                                 4-CO.sub.2 CH.sub.3                                                                           H   H  OCH.sub.3                                                                         OCH.sub.3 CH.sub.3                                 4-CO.sub.2 -i-C.sub.3 H.sub.7                                                                 H   H  CH.sub.3                                                                          CH.sub.3  CH.sub.2 CH.sub.3                        4-CO.sub.2 -i-C.sub.3 H.sub.7                                                                 H   H  OCH.sub.3                                                                         OCH.sub.3 CH.sub. 3                                4-CO.sub.2 -i-C.sub.3 H.sub.7                                                                 H   H  CH.sub.3                                                                          OCH.sub.3 CH.sub.3                                 4-CH.sub.3      H   H  CH.sub.3                                                                          CH.sub.3  CH.sub.3                                 4-CH.sub.3      H   H  OCH.sub.3                                                                         OCH.sub.3 CH.sub.3                                 4-SO.sub.2 N(CH.sub.2 CH.sub.3).sub.2                                                         2-CH.sub.3                                                                        H  CH.sub.3                                                                          OCH.sub.3 CH.sub.3                                 2-N(CH.sub.3).sub.2                                                                           6-CH.sub.3                                                                        H  CH.sub.3                                                                          CH.sub.3  CH.sub.2 CH.sub.3                        4-N(CH.sub.3).sub.2                                                                           H   H  OCH.sub.3                                                                         OCH.sub.3 CH.sub.3                                 4-SO.sub.2 N(CH.sub.3).sub.2                                                                  H   H  CH.sub.3                                                                          OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3      __________________________________________________________________________

                  TABLE X                                                         ______________________________________                                         ##STR44##                                                                    R.sub.1     R.sub.2  Y.sub.1  X.sub.1                                                                              R.sub.12                                 ______________________________________                                        2-C.sub.2 H.sub.5                                                                         2-CH.sub.3                                                                             CH.sub.3 CH.sub.3                                                                             CH.sub.3                                 4-CO.sub.2 C.sub.2 H.sub.5                                                                H        CH.sub.3 CH.sub.3                                                                             CH.sub.3                                 2-CO.sub.2 CH.sub.3                                                                       H        CH.sub.3 CH.sub.3                                                                             CH.sub.3                                 2-SO.sub.2 N(CH.sub.2 CH.sub.3)                                                           H        CH.sub.3 CH.sub.3                                                                             CH.sub.3                                 4-N(CH.sub.2 CH.sub.3)                                                                    H        OCH.sub.3                                                                              OCH.sub.3                                                                            CH.sub.2 CH.sub.3                        2-SO.sub.2 N(CH.sub.3).sub.2                                                              H        CH.sub.3 OCH.sub.3                                                                            CH.sub.3                                 ______________________________________                                    

                  TABLE XI                                                        ______________________________________                                         ##STR45##                                                                    R.sub.1   R.sub.2  Y.sub.1 X.sub.1                                                                              R.sub.12                                    ______________________________________                                        2-n-C.sub.4 H.sub.9                                                                     H        OCH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3                                    4-CO.sub.2 CH.sub.3                                                                     H        OCH.sub.3                                                                             Cl     CH.sub.3                                    2-Cl      H        OCH.sub.3                                                                             OCH.sub.3                                                                            CH.sub.3                                    2-N(CH.sub.3).sub.2                                                                     6-CH.sub.3                                                                             CH.sub.3                                                                              CH.sub.3                                                                             CH.sub.3                                    4-SO.sub.2 N(CH.sub.3).sub.2                                                            H        CH.sub.3                                                                              OCH.sub.3                                                                            CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3         ______________________________________                                    

EXAMPLE 10N-[(4-methoxy-6-methyl-1,3-5-triazin-2-yl)aminocarbonyl]3-pyridinesulfonamide

To 4 ml of 15% aqueous tetrahydrofuran was added with stirring 0.4 g ofmercuric oxide and 0.28 ml of boron-trifluoride etherate. The mixturewas stirred for 20 minutes, and then 0.4 g ofN-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)N'-(3-pyridinylsulfonyl)carbamimidothioicacid, methyl ester was added. The slurry was stirred at room temperaturefor 1 hour, filtered and the solid was washed with 50 ml of water,followed by 40 ml of dichloromethane, and dissolved with 25 ml of 0.1Nsodium hydroxide. The basic solution was filtered and the filtrateacidified with dilute hydrochloric acid to yield the desired product asa precipitate. The solid was filtered off, washed with water, and driedto give 0.2 g of pale yellow solid, m.p. 185°-190° C.

EXAMPLE 11N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-3-pyridinesulfonamide

To 25 ml of 80% aqueous acetonitrile was added with stirring 0.6 g ofmercuric chloride and then 0.34 g ofN-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N'-(3-pyridinylsulfonyl)carbamimidothioicacid, methyl ester. To this mixture, 0.22 g of calcium carbonate wasadded to adjust the pH to 7. The resulting mixture was heated to refluxfor 2 hours, then cooled to room temperature and filtered. The solid wasrinsed with 25 ml of dichloromethane three times, 25 ml of water threetimes, and then dissolved in 30 ml of 0.1N of sodium hydroxide.Acidification of the basic solution with dilute hydrochloric acidyielded the desired product as a precipitate which was filtered off,rinsed with water, and dried at reduced pressure to give 0.2 g of paleyellow solid, m.p. 185°-190° C.

By using the procedures of Examples 10 or 11, the compounds of Table XIIcan be prepared from the appropriately substituted pyridinesulfonylcarbamimidothioic acid esters.

                  TABLE XII                                                       ______________________________________                                         ##STR46##                                                                    R.sub.1     R.sub.2 R.sub.4                                                                              X     Y                                            ______________________________________                                        2-Cl        H       CH.sub.3                                                                             CH.sub.3                                                                            OCH.sub.3                                    2-CH.sub.3  6-CH.sub.3                                                                            H      CH.sub.3                                                                            OCH.sub.3                                    4-CH.sub.3   H      CH.sub.3                                                                             CH.sub.3                                                                            OCH.sub.2 CH.sub.2 OCH.sub.3                 2-CO.sub.2 CH.sub.2 CH.sub.2 Cl                                                            H      H      CH.sub.3                                                                            OCH.sub.3                                    2-CO.sub.2 CH.sub.2 CHCH.sub.2                                                             H      H      CH.sub.3                                                                            OCH.sub.3                                    2-CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                     H      H      OCH.sub.3                                                                           OCH.sub.3                                    2-CO.sub.2 CH.sub.3                                                                        H      H      CH.sub.3                                                                            S(CH.sub.2).sub.2 CO.sub.2 C.sub.2                                            H.sub.5                                      4-CO.sub.2 C.sub.2 H.sub.5                                                                 H      H      OCH.sub.3                                                                           OCH.sub.3                                    2-CO.sub.2 CH.sub.3                                                                        H      H      CH.sub.3                                                                            OCH.sub.3                                    4-OCH.sub.3  H      H      CH.sub.3                                                                            OCH.sub.3                                    4-Cl         H      H      CH.sub.3                                                                            N(CH.sub.3).sub.2                            2-Br         H      H      CH.sub.3                                                                            Cl                                           2-OC.sub.2 H.sub.5                                                                         H      H      CH.sub.3                                                                            SC.sub.2 H.sub.5                             4-Sn-C.sub.4 H.sub.9                                                                       H      H      OCH.sub.3                                                                           OCH.sub.3                                    2-SC.sub.2 H.sub.5                                                                         H      H      CH.sub.3                                                                            OCH.sub.3                                    4-F          H      H      CH.sub.3                                                                            OCH.sub.2 CH.sub.2 CO.sub.2 C.sub.2                                           H.sub.5                                      2-SCH.sub.3  H      H      CH.sub.3                                                                            OCH.sub.3                                    4-Br         H      H      OCH.sub.3                                                                           OCH.sub.3                                    2-n-C.sub.4 H.sub.9                                                                        H      H      OCH.sub.3                                                                           OCH.sub.3                                    2-F          6-Cl   H      OC.sub.2 H.sub.5                                                                    CH.sub.2 OCH.sub.3                           2-Cl         H      H      OCH.sub.3                                                                           OCH.sub.3                                    2-Cl         H      H      CH.sub.3                                                                            CH.sub.2 OCH.sub.3                           2-Cl         H      H      CH.sub.3                                                                            CH.sub.3                                     H            H      H      CH.sub.3                                                                            CH.sub.3                                     H            H      H      OCH.sub.3                                                                           OCH.sub.3                                    2-CO.sub.2 CH.sub.3                                                                        H      H      OCH.sub.3                                                                           OCH                                          2-CO.sub.2 CH.sub.3                                                                        H      H      CH.sub.3                                                                            OCH.sub.3                                    2-CO.sub.2 CH.sub.3                                                                        H      H      CH.sub.3                                                                            CH.sub.3                                     2-CO.sub.2i-C.sub.3 H.sub.7                                                                H      H      CH.sub.3                                                                            CH.sub.3                                     2-CO.sub.2i-C.sub.3 H.sub.7                                                                H      H      CH.sub.3                                                                            OCH.sub.3                                    2-CO.sub.2i-C.sub.3 H.sub.7                                                                H      H      OCH.sub.3                                                                           OCH.sub.3                                    2-CH.sub.3   H      H      OCH.sub.3                                                                           OCH.sub.3                                    2-CH.sub.3   H      H      CH.sub.3                                                                            OCH.sub.3                                    2-CH.sub.3   H      H      CH.sub.3                                                                            CH.sub.3                                     4-Cl         H      H      CH.sub.3                                                                            CH.sub.3                                     4-Cl         H      H      OCH.sub.3                                                                           OCH.sub.3                                    4-CO.sub.2 CH.sub.3                                                                        H      H      CH.sub.3                                                                            CH.sub.3                                     4-CO.sub.2 CH.sub.3                                                                        H      H      CH.sub.3                                                                            OCH.sub.3                                    4-CO.sub.2 CH.sub.3                                                                        H      H      OCH.sub.3                                                                           OCH.sub.3                                    4-CO.sub.2i-C.sub.3 H.sub.7                                                                H      H      CH.sub.3                                                                            CH.sub.3                                     4-CO.sub.2i-C.sub.3 H.sub.7                                                                H      H      OCH.sub.3                                                                           OCH.sub.3                                    4-CO.sub.2i-C.sub.3 H.sub.7                                                                H      H      CH.sub.3                                                                            OCH.sub.3                                    4-CH.sub.3   H      H      CH.sub.3                                                                            CH.sub.3                                     4-CH.sub.3   H      H      OCH.sub.3                                                                           OCH.sub.3                                    2-SO.sub.2 N(CH.sub.3).sub.2                                                               H      H      CH.sub.3                                                                            CH.sub.3                                     2-N(CH.sub.2 CH.sub.3).sub.2                                                               6-CH.sub.3                                                                           H      CH.sub.3                                                                            OCH.sub.3                                    4-SO.sub.2 N(CH.sub.2 CH.sub.3).sub.2                                                      H      H      OCH.sub.3                                                                           OCH.sub.3                                    4-N(CH.sub.2 CH.sub.3).sub.2                                                               H      H      CH.sub.3                                                                            CH.sub.3                                     ______________________________________                                    

EXAMPLE 12N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-3-pyridinesulfonamide

To 8 ml of 15% aqueous tetrahydrofuran was added with stirring 0.8 g ofmercuric acid oxide and 0.56 ml of borontrifluoride etherate. Themixture was stirred for 20 minutes, and then 0.8 g ofN-(4,6-dimethoxypyrimidin-2-yl)-N'-(3-pyridinylsulfonyl)carbamimidothioicacid, methyl ester was added. The slurry was stirred at room temperaturefor 1 hour, filtered, and the solid was rinsed with 50 ml of water,followed by 40 ml of dichloromethane, and dried to give 0.3 g of thedesired product, m.p. 176° C. dec.

By using the procedure of Example 12, the compounds of Tables XIII, XIVand XV can be prepared from the appropriately substitutedpyridinesulfonylcarbamimidothioic acid esters.

                                      TABLE XIII                                  __________________________________________________________________________     ##STR47##                                                                    R.sub.1           R.sub.2                                                                             R.sub.4                                                                            X     Y                                          __________________________________________________________________________    2-Cl              H     CH.sub.3                                                                           CH.sub.3                                                                            OCH.sub.3                                  4-Cl              H     H    CH.sub.3                                                                            OCH.sub.3                                  2-CH.sub.3        6-CH.sub.3                                                                          H    CH.sub.3                                                                            OCH.sub.3                                  4-CH.sub.3        H     CH.sub.3                                                                           CH.sub.3                                                                            OCH.sub.2 CH.sub.2 OCH.sub.3               2-CO.sub.2 CH.sub.2 CHCH.sub.2                                                                  H     H    CH.sub.3                                                                            OCH.sub.3                                  2-CO.sub.2 CHCHCH(CH.sub.2).sub.2 CH.sub.3                                                      H     H    CH.sub.3                                                                            OCH.sub.3                                  2-CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                          H     H    CH.sub.3                                                                            CH.sub.3                                   2-CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3                                                 H     H    CH.sub.3                                                                            OCH.sub.3                                  2-CO.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                 H     H    CH.sub.3                                                                            OCH.sub.3                                  2-CO.sub. 2 CH.sub.2 CH.sub.2 Cl                                                                H     H    OCH.sub.3                                                                           OCH.sub.3                                  2-CO.sub.2 CH.sub.3                                                                             H     H    CH.sub.3                                                                            S(CH.sub.2).sub.2 CO.sub.2 C.sub.2                                            H.sub.5                                    4-CO.sub.2 C.sub.2 H.sub.5                                                                      H     H    OCH.sub.3                                                                           OCH.sub.3                                  4-OCH.sub.3       H     H    CH.sub.3                                                                            OCH.sub.3                                  2-OCH.sub.3       H     H    OC.sub.2 H.sub.5                                                                    OCH.sub.3                                  4-Cl              H     H    CH.sub.3                                                                            N(CH.sub.3).sub.2                          4-Br              H     H    CH.sub.3                                                                            Cl                                         4-OC.sub.2 H.sub.5                                                                              H     H    CH.sub.3                                                                            SC.sub.2 H.sub.5                           4-Sn-C.sub.4 H.sub.9                                                                            H     H    OCH.sub.3                                                                           OCH.sub.3                                  2-SC.sub.2 H.sub.5                                                                              H     H    CH.sub.3                                                                            OCH.sub.3                                  4-F               H     H    CH.sub.3                                                                            OCH.sub.2 CH.sub.2 CO.sub.2 C.sub.2                                           H.sub.5                                    2-SCH.sub.3       H     H    CH.sub.3                                                                            OCH.sub.3                                  2-Br              H     H    OCH.sub.3                                                                           OCH.sub.3                                  2-n-C.sub.4 H.sub.9                                                                             H     H    OCH.sub.3                                                                           OCH.sub.3                                  4-F               6-Cl  H    OC.sub.2 H.sub.5                                                                    CH.sub.2 OCH.sub.3                         2-SO.sub.2 N(CH.sub.3).sub.2                                                                    6-CH.sub.3                                                                          H    CH.sub.3                                                                            OCH.sub.3                                  2-N(CH.sub.2 CH.sub.3)                                                                          H     H    OCH.sub.3                                                                           OCH.sub.3                                  4-SO.sub.2 N(CH.sub.3).sub.2                                                                    2-CH.sub.3                                                                          H    CH.sub.3                                                                            CH.sub.3                                   4-SO.sub.2 N(CH.sub.3 ).sub.2                                                                   H     H    CH.sub.3                                                                            OCH.sub.3                                  2-Cl              4-Cl  H    OCH.sub.3                                                                           OCH.sub.3                                  2-Cl              4-Cl  H    CH.sub.3                                                                            OCH.sub.3                                  H                 H     H    CH.sub.3                                                                            CH.sub.3                                   H                 H     H    OCH.sub.3                                                                           OCH.sub.3                                  2-Cl              H     H    OCH.sub.3                                                                           OCH.sub.3                                  2-Cl              H     H    CH.sub.3                                                                            CH.sub.2 OCH.sub.3                         2-Cl              H     H    CH.sub.3                                                                            CH.sub.3                                   2-CO.sub.2 CH.sub.3                                                                             H     H    OCH.sub.3                                                                           OCH                                        2-CO.sub.2 CH.sub.3                                                                             H     H    CH.sub.3                                                                            OCH.sub.3                                  2-CO.sub.2 CH.sub.3                                                                             H     H    CH.sub.3                                                                            CH.sub.3                                   2-CO.sub.2i-C.sub.3 H.sub.7                                                                     H     H    CH.sub.3                                                                            CH.sub.3                                   2-CO.sub.2i-C.sub.3 H.sub.7                                                                     H     H    CH.sub.3                                                                            OCH.sub.3                                  2-CO.sub.2i-C.sub.3 H.sub.7                                                                     H     H    OCH.sub.3                                                                           OCH.sub.3                                  2-CH.sub.3        H     H    OCH.sub.3                                                                           OCH.sub.3                                  2-CH.sub.3        H     H    CH.sub.3                                                                            OCH.sub.3                                  2-CH.sub.3        H     H    CH.sub.3                                                                            CH.sub.3                                   4-Cl              H     H    CH.sub.3                                                                            CH.sub.3                                   4-Cl              H     H    OCH.sub.3                                                                           OCH.sub.3                                  4-CO.sub.2 CH.sub.3                                                                             H     H    CH.sub.3                                                                            CH.sub.3                                   4-CO.sub.2 CH.sub.3                                                                             H     H    CH.sub.3                                                                            OCH.sub.3                                  4-CO.sub.2 CH.sub.3                                                                             H     H    OCH.sub.3                                                                           OCH.sub.3                                  4-CO.sub.2i-C.sub.3 H.sub.7                                                                     H     H    CH.sub.3                                                                            CH.sub.3                                   4-CO.sub.2i-C.sub.3 H.sub.7                                                                     H     H    OCH.sub.3                                                                           OCH.sub.3                                  4-CO.sub.2i-C.sub.3 H.sub.7                                                                     H     H    CH.sub.3                                                                            OCH.sub.3                                  4-CH.sub.3        H     H    CH.sub.3                                                                            CH.sub.3                                   4-CH.sub.3        H     H    OCH.sub.3                                                                           OCH.sub.3                                  __________________________________________________________________________

                  TABLE XIV                                                       ______________________________________                                         ##STR48##                                                                    R.sub.1       R.sub.2   X.sub.1    Y.sub.1                                    ______________________________________                                        2-F           H         CH.sub.3   CH.sub.3                                   2-C.sub.2 H.sub.5                                                                           H         CH.sub.3   OCH                                        2-Cl          H         CH.sub.3   OCH.sub.3                                  4-C.sub.2 H.sub.5                                                                           2-CH.sub.3                                                                              CH.sub.3   CH.sub.3                                   4-Br          6-Cl      CH.sub.3   OCH.sub.3                                  4-CO.sub.2 C.sub.2 H.sub.5                                                                  H         CH.sub.3   CH.sub.3                                   2-CO.sub.2 CH.sub.3                                                                         H         CH.sub.3   CH.sub.3                                   4-OCH.sub.3   H         CH.sub.3   OCH.sub.3                                  2-Br          H         OCH.sub.3  OCH.sub.3                                  2-SO.sub.2 N(CH.sub.3).sub.3                                                                H         CH.sub.3   OCH.sub.3                                  4-N(CH.sub.2 CH.sub.3).sub.2                                                                H         OCH.sub.3  OCH.sub.3                                  2-SCH.sub.3   H         CH.sub.3   OCH.sub.3                                  ______________________________________                                    

                  TABLE XV                                                        ______________________________________                                         ##STR49##                                                                    R.sub.1       R.sub.2   Y.sub.1    X.sub.1                                    ______________________________________                                        4-F           H         OCH.sub.3  C.sub.2 H.sub.5                            2-Cl          H         OCH.sub.3  OCH.sub.3                                  2-N(CH.sub.3).sub.2                                                                         6-CH.sub.3                                                                              CH.sub.3   CH.sub.3                                   4-SO.sub.2 N(CH.sub.3).sub.2                                                                H         CH.sub.3   OCH.sub.3                                  ______________________________________                                    

Agriculturally useful acid addition salts of appropriateN-[(triazinyl)aminocarbonyl]pyridinesulfonamides orN-[(pyrimidinyl)aminocarbonyl]pyridinesulfonamides can be prepared asdescribed in Equation 14 by treating the appropriateN-aminocarbonylpyridinesulfonamide with an equivalent amount of asuitable mineral or organic acid in a solvent such as methanol orethanol and removing the solvent to yield the desired acid salt. By thismethod, acid addition salts can be prepared with anions such as: Cl⁻,Br⁻, NO₃ ⁻, HSO₄ ⁻, SO₄ ⁼, H₂ PO₄ ⁻, HPO₄ ⁼, CCl₃ COO⁻, CH₃ SO₃ ⁻, p-CH₃C₆ H₄ SO₃, and C₁₂ H₂₅ SO₃ ⁻.

Agriculturally useful alkali metal salts can be prepared as described inEquation 12 by the reaction of a suitableN-[(triazinyl)-aminocarbonyl]pyridinesulfonamide or aN-(pyrimidinylaminocarbonyl)pyridinesulfonamide with an equivalent of asuitable alkali metal alkoxide in an alcohol solvent (for example,sodium methoxide in methanol) removal of solvent and trituration usuallyperformed with a solvent such as ethylacetate. In this manner, a varietyof alkali metal salts can be made with cations such as: Li⁺, Na⁺, K⁺,Ca⁺⁺.

It should be noted that there is not intent to be limited to the saltswhich are mentioned above.

EXAMPLE 13 2-Chloro-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-3-pyridinesulfonamide, sodium salt.

To a stirred suspension of 1.0 g of2-chloro-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]3-pyridinesulfonamidein 25 ml of methanol is added 0.15 g of sodium methoxide. The resultingsolution is heated on a steam bath for 5 minutes, cooled and the solventremoved in vacuo to yield the desired salt Trituration with ethylacetateyields the sodium salt of2-chloro-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-3-pyridinesulfonamideas a colorless solid.

As described in Equation 13 and further illustrated in Example 14,reaction of a suitable N-(triazinylaminocarbonyl)pyridinesulfonamide ora N-(pyrimidinylaminocarbonyl)pyridinesulfonamide with an equivalent ofan appropriate amine in a solvent such as methylene chloride or methanolfollowed by removal of this solvent yields agriculturally usefulammonium salts of N-(aminocarbonyl)pyridinesulfonamides. Amines such asammonia, ethylamine, diethylamine, triethylamine, trimethylamine,diethanolamine, triethanolamine, isopropylamine, pyridine,dimethylaniline, laurylamine or di-n-butylamine may be employed.

EXAMPLE 142-Chloro-N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-3-pyridinesulfonamide,triethanolamine salt

To a stirring suspension of 1.0 g of2-chloro-N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-3-pyridinesulfonamidein 25 ml of methylene chloride is added 0.42 g of triethanolamine. Thesolvent is removed in vacuo to yield as product the desiredtriethanolamine salt.

By using an appropriately substituted N-alkylpyridinesulfonylcarbamylchloride or thiocarbamylchloride and an appropriate aminopyrimidine oraminotriazine, the compounds of Formula I set forth in Table XVI can beprepared by the procedure of Equation 5. For example,2-chloro-N-[N-(4-methoxy6-methylpyrimidine-2-yl)-N-methylaminocarbonyl]-N-methyl-3-pyridinesulfonamidecan be prepared by reacting 2.1 g ofN-[(2-chloro-3-pyridine)sulfonyl]-N'-methylcarbamylchloride in 50 ml oftetrahydrofuran containing 1.0 g of triethylamine to 1.5 g of2-methylamino-4-methoxy-6-methylpyrimidine. That mixture can be stirredat reflux for several hours, the precipitated salts can be filtered offand the filtrate can be concentrated to yield the desired product.

                  TABLE XVI                                                       ______________________________________                                         ##STR50##                                                                    R.sub.1      R.sub.2 R.sub.4                                                                              W X    Y      Z                                   ______________________________________                                        2-Cl         H       H      O OCH.sub.3                                                                          OCH.sub.3                                                                            CH                                  2-Cl         H       H      O CH.sub.3                                                                           OCH.sub.3                                                                            N                                   2-Cl         H       CH.sub.3                                                                             S  CH.sub.3                                                                          OCH.sub.3                                                                            CH                                  2-Cl         H       H      O CH.sub.3                                                                           OCH.sub.3                                                                            CH                                  2-CO.sub.2 CH.sub.3                                                                        H       H      O CH.sub.3                                                                           N(CH.sub.3).sub.2                                                                    CH                                  2-CO.sub.2 CH.sub.3                                                                        H       H      O CH.sub.3                                                                           N(CH.sub.3).sub.2                                                                    N                                   4-OC.sub.2 H.sub.5                                                                         6-CH.sub.3                                                                            H      O CH.sub.3                                                                           OCH.sub.3                                                                            CH                                  2-SO.sub.2 N(CH.sub.3)CH.sub.2 CH.sub.3                                                    H       H      S  CH.sub.3                                                                          OCH.sub.3                                                                            CH                                  4-N(CH.sub.2 CH.sub.3).sub.2                                                               H       CH.sub.3                                                                             O OCH.sub. 3                                                                         OCH.sub.3                                                                            N                                   2-SCH.sub.3  H       H      O CH.sub.3                                                                           CH.sub.3                                                                             N                                   4-Br         H       H      O CH.sub.3                                                                           N(CH.sub.3).sub.2                                                                    CH                                  ______________________________________                                    

Formulations

Useful formulations of the compounds of Formula I can be prepared inconventional ways. They include dusts, granules, pellets, solutions,suspensions, emulsions, wettable powders, emulsifiable concentrates andthe like. Many of these may be applied directly. Sprayable formulationscan be extended in suitable media and used at spray volumes of from afew liters to several hundred liters per hectare. High strengthcompositions are primarily used as intermediates for furtherformulation. The formulations, broadly, contain about 0.1% to 99% byweight of active ingredient(s) and at least one of (a) about 0.1% to 20%surfactant(s) and (b) about 1% to 99.9% solid or liquid diluent(s). Morespecifically, they will contain these ingredients in the followingapproximate proportions:

                  TABLE XVII                                                      ______________________________________                                                    Active  Weight Percent*                                                       Ingredient                                                                            Diluent(s)                                                                              Surfactant(s)                                   ______________________________________                                        Wettable Powders                                                                            20-90      0-74      1-10                                       Oil Suspensions,                                                                            3-50      40-95      0-15                                       Emulsions, Solutions,                                                         (including Emulsifiable                                                       Concentrates)                                                                 Aqueous Suspension                                                                          10-50     40-84      1-20                                       Dusts          1-25     70-99     0-5                                         Granules and Pellets                                                                        0.1-95      5-99.9   0-15                                       High Strength 90-99      0-10     0-2                                         Compositions                                                                  ______________________________________                                         *Active ingredient plus at least one of a Surfactant or a Diluent equals      100 weight percent.                                                      

Lower or higher levels of active ingredient can, of course, be presentdepending on the intended use and the physical properties of thecompound. Higher ratios of surfactant to active ingredient are sometimesdesirable, and are achieved by incorporation into the formulation or bytank mixing.

Typical solid diluents are described in Watkins, et al., "Handbook ofInsecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books,Caldwell, N.J., but other solids, either mined or manufactured, may beused. The more absorptive diluents are preferred for wettable powdersand the denser ones for dusts. Typical liquid diluents and solvents aredescribed in Marsden, "Solvents Guide," 2nd Ed., Interscience, New York,1950. Solubility under 0.1% is preferred for suspension concentrates;solution concentrates are preferably stable against phase separation at0° C. "McCutcheon's Detergents and Emulsifiers Annual", MC PublishingCorp., Ridgewood, N.J., as well as Sisely and Wood, "Encyclopedia ofSurface Active Agents", Chemical Publishing Co., Inc., New York, 1964,list surfactants and recommended uses. All formulations can containminor amounts of additives to reduce foaming, caking, corrosion,microbiological growth, etc.

The methods of making such compositions are well known. Solutions areprepared by simply mixing the ingredients. Fine solid compositions aremade by blending and, usually, grinding as in a hammer or fluid energymill. Suspensions are prepared by wet milling (see, for example,Littler, U.S. Pat. No. 3,060,084). Granules and pellets may be made byspraying the active material upon preformed granular carriers or byagglomeration techniques. See J. E. Browning, "Agglomeration", ChemicalEngineering, Dec. 4, 1967, pp. 147ff. and "Perry's Chemical Engineer'sHandbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-57ff.

For further information regarding the art of formulation, see forexample:

H. M. Loux, U.S. Pat. No. 3,235,361, Feb. 15, 1966, Col. 6, line 16through Col. 7, line 19 and Examples 10 through 41;

R. W. Luckenbaugh, U.S. Pat. No. 3,309,192, Mar. 14, 1967, Col. 5, line43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58,132, 138-140, 162-164, 166, 167 and 169-182;

H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, June 23, 1959, Col. 3,line 66 through Col. 5, line 17 and Examples 1-4;

G. C. Klingman, "Weed Control as a Science", John Wiley & Sons, Inc.,New York, 1961, pp. 81-96; and

J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., BlackwellScientific Publications, Oxford, 1968, pp. 101-103.

In the following examples, all parts are by weight unless otherwiseindicated.

EXAMPLE 15

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        2-Chloro-N--[(4-methoxy-6-methylpyrimidin-2-yl)amino-                                                       80%                                             carbonyl]-3-pyridinesulfonamide                                               sodium alkylnaphthalenesulfonate                                                                             2%                                             sodium ligninsulfonate         2%                                             synthetic amorphous silica     3%                                             kaolinite                     13%                                             ______________________________________                                    

The ingredients are blended, hammer-milled until all the solids areessentially under 50 microns, reblended, and packaged.

EXAMPLE 16

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        2-Chloro-N--[(4,6-dimethoxypyrimidin-2-yl)amino-                                                          50%                                               carbonyl]-3-pyridinesulfonamide                                               sodium alkylnaphthalenesulfonate                                                                           2%                                               low viscosity methyl cellulose                                                                             2%                                               diatomaceous earth          46%                                               ______________________________________                                    

The ingredients are blended, coarsely hammer-milled and then air-milledto produce particles essentially all below 10 microns in diameter. Theproduct is reblended before packaging.

EXAMPLE 17

    ______________________________________                                        Granule                                                                       ______________________________________                                        Wettable Powder of Example 16                                                                         5%                                                    attapulgite granules   95%                                                    (U.S.S. 20-40 mesh; 0.84-0.42 mm)                                             ______________________________________                                    

A slurry of wettable powder containing 25% solids is sprayed on thesurface of attapulgite granules in a double-cone blender. The granulesare dried and packaged.

EXAMPLE 18

    ______________________________________                                        Extruded Pellet                                                               ______________________________________                                        2-Chloro-N--[(4,6-dimethylpyrimidin-2-yl)amino-                                                          25%                                                carbonyl-3-pyridinesulfonamide                                                anhydrous sodium sulfate   10%                                                crude calcium ligninsulfonate                                                                             5%                                                sodium alkylnaphthalenesulfonate                                                                          1%                                                calcium/magnesium bentonite                                                                              59%                                                ______________________________________                                    

The ingredients are blended, hammer-milled and then moistened with about12% water. The mixture is extruded as cylinders about 3 mm diameterwhich are cut to produce pellets about 3 mm long. These may be useddirectly after drying, or the dried pellets may be crushed to pass aU.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S.No. 40 sieve (0.42 mm openings) may be packaged for use and the finesrecycled.

EXAMPLE 19

    ______________________________________                                        Oil Suspension                                                                ______________________________________                                        2-Chloro-N--[(4-methoxy-6-methyl-1,3,5-triazin-                                                          25%                                                2-yl)aminocarbonyl]-3-pyridinesulfonamide                                     polyoxyethylene sorbitol hexaoleate                                                                       5%                                                highly aliphatic hydrocarbon oil                                                                         70%                                                ______________________________________                                    

The ingredients are ground together in a sand mill until the solidparticles have been reduced to under about 5 microns. The resultingthick suspension may be applied directly, but preferably after beingextended with oils or emulsified in water.

EXAMPLE 20

    ______________________________________                                        Wettab1e Powder                                                               ______________________________________                                        2-Chloro-N--[(4,6-dimethoxy-1,3,5-triazin-2-yl)-                                                         20%                                                aminocarbonyl]-3-pyridinesulfonamide                                          sodium alkylnaphthalenesulfonate                                                                          4%                                                sodium ligninsulfonate      4%                                                low viscosity methyl cellulose                                                                            3%                                                attapulgite                69%                                                ______________________________________                                    

The ingredients are thoroughly blended. After grinding in a hammer-millto produce particles essentially all below 100 microns, the material isreblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) andpackaged.

EXAMPLE 21

    ______________________________________                                        Low Strength Granule                                                          ______________________________________                                        2-Chloro-N--[(4,6-dimethyl-1,3,5-triazin-2-yl)-                                                           1%                                                aminocarbonyl]-3-pyridinesulfonamide                                          N,N--dimethylformamide      9%                                                attapulgite granules       90%                                                (U.S.S. 20-40 sieve)                                                          ______________________________________                                    

The active ingredient is dissolved in the solvent and the solution issprayed upon dedusted granules in a double cone blender. After sprayingof the solution has been completed, the blender is allowed to run for ashort period and then the granules are packaged.

EXAMPLE 22

    ______________________________________                                        Aqueous Suspension                                                            ______________________________________                                        2-Chloro-N--[(4-methoxy-6-methyl-1,3,5-triazin-                                                           40%                                               2-yl)aminocarbonyl]-3-pyridinesulfonamide                                     polyacrylic acid thickener  0.3%                                              dodecylphenol polyethylene glycol ether                                                                   0.5%                                              disodium phosphate          1%                                                monosodium phosphate        0.5%                                              polyvinyl alcohol           1.0%                                              water                       56.7%                                             ______________________________________                                    

The ingredients are blended and ground together in a sand mill toproduce particles essentially all under 5 microns in size.

EXAMPLE 23

    ______________________________________                                        Solution                                                                      ______________________________________                                        2-Chloro-N--[(4-methoxy-6-methylpyrimidin-2-yl)-                                                           5%                                               aminocarbonyl]-3-pyridinesulfonamide sodium salt                              water                       95%                                               ______________________________________                                    

The salt is added directly to the water with stirring to produce thesolution, which may then be packaged for use.

EXAMPLE 24

    ______________________________________                                        Low Strength Granule                                                          ______________________________________                                        2-Chloro-N--[(4,6-dimethyl-1,3,5,triazin-2-yl)-                                                           0.1%                                              aminocarbonyl]-3-pyridinesulfonamide                                          attapulgite granules       99.9%                                              (U.S.S. 20-40 mesh)                                                           ______________________________________                                    

The active ingredient is dissolved in a solvent and the solution issprayed upon dedusted granules in a double-cone blender. After sprayingof the solution has been completed, the material is warmed to evaporatethe solvent. The material is allowed to cool and then packaged.

EXAMPLE 25

    ______________________________________                                        Granule                                                                       ______________________________________                                        2-Chloro-N--[(N--4,6-dimethoxy-1,3,5-triazin-                                                            80%                                                2-yl)aminocarbonyl]-3-pyridinesulfonamide                                     wetting agent               1%                                                crude ligninsulfonate salt (containing                                                                   10%                                                5-20% of the natural sugars)                                                  attapulgite clay            9%                                                ______________________________________                                    

The ingredients are blended and milled to pass through a 100 meshscreen. This material is then added to a fluid bed granulator, the airflow is adjusted to gently fluidize the material, and a fine spray ofwater is sprayed onto the fluidized material. The fluidization andspraying are continued until granules of the desired size range aremade. The spraying is stopped, but fluidization is continued, optionallywith heat, until the water content is reduced to the desired level,generally less than 1%. The material is then discharged, screened to thedesired size range, generally 14-100 mesh (1410-149 microns), andpackaged for use.

EXAMPLE 26

    ______________________________________                                        High Strength Concentrate                                                     ______________________________________                                        2-Chloro-N--[(4,6-dimethoxypyrimidin-2-yl)-                                                               99%                                               aminocarbonyl-3-pyridinesulfonamide                                           silica aerogel              0.5%                                              synthetic amorphous silica  0.5%                                              ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produce amaterial essentially all passing a U.S.S. No. 50 screen (0.3 mmopening). The concentrate may be formulated further if necessary.

EXAMPLE 27

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        2-Chloro-N--[(4,6-dimethylpyrimidin-2-yl)-                                                                90%                                               aminocarbonyl]-3-pyridinesulfonamide                                          dioctyl sodium sulfosuccinate                                                                             0.1%                                              synthetic fine silica       9.9%                                              ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produceparticles essentially all below 100 microns. The material is siftedthrough a U.S.S. No. 50 screen and then packaged.

EXAMPLE 28

    ______________________________________                                        Wettable powder                                                               ______________________________________                                        2-Chloro-N--[(4-methoxy-6-methyl-1,3,5-triazin-                                                          40%                                                2-yl)aminocarbonyl]-3-pyridinesulfonamide                                     sodium ligninsulfonate     20%                                                montmorillonite clay       40%                                                ______________________________________                                    

The ingredients are thoroughly blended, coarsely hammer-milled and thenair-milled to produce particles essentially all below 10 microns insize. The material is reblended and then packaged.

EXAMPLE 29

    ______________________________________                                        Oil Suspension                                                                ______________________________________                                        2-Chloro-N--[(4,6-dimethyl-1,3,5-triazin-yl)-                                                            35%                                                aminocarbonyl]-3-pyridinesulfonamide                                          blend of polyalcohol carboxylic                                                                           6%                                                esters and oil soluble petroleum                                              sulfonates                                                                    xylene                     59%                                                ______________________________________                                    

The ingredients are combined and ground together in a sand mill toproduce particles essentially all below 5 microns. The product can beused directly, extended with oils, or emulsified in water.

EXAMPLE 30

    ______________________________________                                        Dust                                                                          ______________________________________                                        2-Chloro-N--[(4,6-dimethoxy-1,3,5-triazin-2-yl)-                                                         10%                                                aminocarbonyl]-3-pyridinesulfonamide                                          attapulgite                10%                                                Pyrophyllite               80%                                                ______________________________________                                    

The active ingredient is blended with attapulgite and then passedthrough a hammer-mill to produce particles substantially all below 200microns. The ground concentrate is then blended with powderedpyrophyllite until homogeneous.

UTILITY

The compounds of the present invention are active herbicides. They haveutility for broad-spectrum pre- and/or post-emergence weed control inareas where complete control of all vegetation is desired, such asaround fuel storage tanks, ammunition depots, industrial storage areas,oil-well sites, drive-in theaters, around billboards, highway andrailroad structures. By properly selecting rate, time and method ofapplication, compounds of this invention may also be used to modifyplant growth beneficially, or to selectively control weeds in crops suchas rice and wheat.

The precise amount of the compounds of Formula I to be used in any givensituation will vary according to the particular end result desired, theamount of foliage present, the crop species involved, the types of weedsto be controlled, the soil type, the formulation and mode ofapplication, weather conditions, etc. Since so many variables play arole, it is not possible to state a rate of application suitable for allsituations. Broadly speaking, the compounds of this invention are usedat levels of about (0.01 to 20 kg/ha) with a preferred range of (0.03 to10 kg/ha). In general, the lower rates of application from within thisrange are suggested for use on lighter soils and/or those having a loworganic matter content, for selective weed control or for plant growthregulation, whereas the higher rates will be selected for adverseconditions or where extended persistence in soil is desired.

The compounds of the invention may be used in combination with any othercommercial herbicide examples of which are those of the triazine,triazole, uracil, urea, amide, diphenylether, carbamate bipyridyliumtypes.

The compounds of Formula I may be combined with other herbicides and areparticularly useful in combination with3-(3,4-dichlorophenyl)-1,1-dimethyl urea; the triazines such as2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine: the uracils suchas 5-bromo-3-secbutyl-6-methyluracil; N-(phosphonomethyl)glycine;3-cyclohexyl-1-methyl-6-dimethylamino-s-triazine-2,4-(1H,3H)-dione;N,N-dimethyl-2,2-diphenylacetamide; 2,4-dichlorophenoxyacetic acid (andclosely related compounds); 4-chloro-2-butynyl-3-chlorophenylcarbamate;diisopropylthiolcarbamic acid, ester with 2,3-dichloroallyl alcohol;diisopropylthiolcarbamic acid, S-(2,3,3-trichloroallyl)ester;ethyl-N-(benzoyl-N-(3,4-dichlorophenyl)-2-aminopropionate;1,2-dimethyl-3,5-diphenylpyrazolium methylsulfate; methyl2-[4-(2,4-dichlorophenoxy)-phenoxy]propanoate;4-amino-6-tert-butyl-3-(methylthio)-1,2,4-triazin-5(4H)-one;3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea;3-isopropyl-1H-2,1,3-benzothiodiazin-(4)-3H-one-2,2-dioxide;α,α,α-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine;1,1'-dimethyl-4,4'-bipyridinium ion; monosodium methanearsonate;2-chloro-2',6'-diethyl(methoxymethyl)acetanilide; and1,1-dimethyl-3-(α,α,α-trifluoro-m-tolyl)urea.

The activity of these compounds was discovered in greenhouse tests. Thetests are described and the data resulting from them are shown below.

O=no effect

10=maximum effect

C=chlorosis or necrosis

D=defoliation

E=emergence inhibition

G=growth retardation

H=formative effects

U=unusual pigmentation

S=albinism

X=axillary stimulation

6Y=abscised buds or flowers

6F=delayed flowering.

Test A

Seeds of crabgrass (Digitaria spp.), barnyardgrass (Echinochloacrusgalli), wild oats (Avena fatua), cassia (Cassia tora), morningglory(Ipomoea sp.), cocklebur (Xanthium spp.), sorghum, corn, soybean, rice,wheat and nutsedge tubers (Cyperus rotundus) were planted in a growthmedium and treated pre-emergence with the chemicals dissolved in a nonphytotoxic solvent solution of the compounds of Table XVIII. At the sametime, cotton having five leaves (including cotyledonary ones), bushbeans with the third trifoliate leaf expanding, crabgrass, barnyardgrassand wild oats with two leaves, cassia with three leaves (includingcotyledonary ones), morningglory and cocklebur with four leaves(including the cotyledonary ones), sorghum and corn with four leaves,soybean with two cotyledonary leaves, rice with three leaves, wheat withone leaf, and nutsedge with three to five leaves were sprayed with anon-phytotoxic solvent solution of the compounds of Table XVIII. Othercontainers of the above untreated weeds and crops were treated pre- orpost-emergence with the same non-phytotoxic solvent so as to provide asolvent control. A set of untreated control plants was also included forcomparison. Pre-emergence and post-emergence treated plants and controlswere maintained in a greenhouse for sixteen days, then all treatedplants were compared with their respective controls and rated visuallyfor response to treatment. The data in Table XVIII shows that thecompounds of this invention are very effective as herbicides and oftencause little or no injury to crops such as wheat and rice.

    TABLE XVIII      POSTEMERGENCE      MORN-     BARN-       Rate BUSH COT- ING- COCKLE-     NUT- CRAB- YARD- WILD   SOY-  SOR-  kg/ha BEAN TON GLORY BUR CASSIA     SEDGE GRASS GRASS OATS WHEAT CORN BEAN RICE GHUM      ##STR51##      0.4 9C 9C 10C 10C 9C 10C 9C 10C 2C,5G 5C,7G 10C 9C 9C 9C      ##STR52##      0.4 9C 9C 10C 10C 9C 10C 9C 10C 5C,9G 5C,8G 10C 9C 9C 10C      ##STR53##     0.4 9D 2C 9G 5C 8G 3C 7G 3C 3C 1C 2G 2C 5H 0 0 7H 2C 5G 1C 6G 3C      ##STR54##      0.4 5C 8G 6Y 4C 8G 1C 6G 3C 8G 3C 8G 9G 1C 4G 2C 8H 1C 1C 2U 8H 3C 7G     3C 7G 2C 7G      ##STR55##      0.4 4C 8G 6Y 4C 8G 1C 1C 3C 0 0 2C 0 0 1C 3H 2C 5G 1C 6G 1C 3G      ##STR56##      0.4 9D 9G 6Y 5C 9G 10C 9C 3C 7G 2C 8G 1C 2C 8H 1C 2G 3G 2U 8G 5C 8G 5C     7G 5C 8G      ##STR57##      0.4 3S 7G 6Y 5C 8G 9C 9C 2C 8G 7G 2G 2C 9H 0 0 5C 9G 2C 7G 2C 6G 3G      ##STR58##      0.4 9C 9C 9C 10C 10C 9C 9C 9C 3C 7G 3C 7G 6U 9G 5C 9G 5C 9G 9C      ##STR59##      0.4 6C 9G 6Y 6C 8G 10C 10C 5C 9G 2C 7G 6G 5C 9H 2C 3C 9U 9C 5C 9G 6C 9G     2C 8G      ##STR60##      0.4 4C 9G 6Y 3C 6G 3C 8G 2C 8H 2C 5G 2C 8G 9C 4C 9H 2C 2C 9C 4C 4C 4C      ##STR61##      0.4 3S 5G 6Y 2C 2C 5G 1C 1C 0 3G 0 0 0 0 0 0 0      ##STR62##      2 1C 3G 3C 4G 1C 3C 9G 2C 0 0 0 0 0 1G 1C 7G 3G      ##STR63##      2 5C 8G 6Y 5C 9G 9C 10C 3C 8G 5C 9G 1C 5G 1C 3G 4G 0 1C 3G 2C 9G 2C 9G     4G      ##STR64##      2 4C 7G 6Y 2C 4H 0 3C 9G 1C 1C 5G 0 0 0 0 2G 3C 7G -- 2G      ##STR65##      2 4C 6G 6Y 5C 9G 5C 9G 3C 9G 0 0 0 0 0 0 0 2C 3H 0 0      ##STR66##      2 3C 7G 6Y 4C 9G 3C 7H 2C 8G 2C 7G 0 0 0 0 0 3C 7G 7G 0      ##STR67##      2 2G 0 0 0 0 0 0 0 0 0 0 0 0 0      ##STR68##      2 2C 2C 2H 0 0 0 0 0 0 0 0 0 0 0 0      ##STR69##      2 2C 3H 2C 3H 2C 6H 7H 1C 0 0 0 0 0 0 0 0 0        PREEMERGENCE   MORN-             Rate ING COCKLE-  NUT-  BARNYARD     WILD  kg/ha GLORY BUR CASSIA SEDGE CRABGRASS GRASS OATS WHEAT CORN     SOYBEAN RICE SORGHUM      ##STR70##      0.4 9C 9H 3C,9G 8G 4C,9G 10C 9H 9H 10E 9H 10E 10H      ##STR71##      0.4 9G 9H 5C,9G 10E 5C,9G 10H 5C,9G 10E 10E 9H 10E 10H      ##STR72##      0.4 2G 1C 3C 1C 4G 2G 1C 6G 0 0 2C 3G 2C 3G 3C 3C 6G      ##STR73##      0.4 8G 8G 8G 10E 1C 5G 3C 9H 1C 5G 7G 9G 9H 10E 1C 9G      ##STR74##      0.4 2C 0 2C 1C 5G 2G 1C 0 0 1C 2G 1C 1C 5G 1C 2G      ##STR75##      0.4 9G 8G 8G 10E 2G 2C 8H 1C 5G 1C 5G 1C 9G 2C 5H 9H 1C 9G      ##STR76##      0.4 9G 3G 1C 4G 0 0 4H 0 0 1C 3G 2C 1C 3H 2G      ##STR77##      0.4 9G 9G 9G 10E 9H 5C 9H 2C 7G 9H 10E 9H 10E 9H      ##STR78##      0.4 9C 9G 9G 4G 4G 9H 4G 2C 9H 10E 9H 10E 5C 9H      ##STR79##      0.4 6G 0 2C 5G 0 0 2C 9H 0 8H 3C 9G 1C 9H 2C 9G      ##STR80##      0.4 3G 0 0 0 0 0 0 0 0 0 0 0      ##STR81##      2 6G 8G 1C 8G 0 0 0 4G 7G 0 2H 2G 0      ##STR82##      2 9G 10E 1C 9G 10E 5G 3C 8H 8G 8G 9G 9H 10E 2C 9H      ##STR83##      2 8G 1C 2C 7G 0 0 1C 0 0 2C 7G 2C 1C 1C      ##STR84##      2 7G 7G 2C 4G 2G 2G 0 0 5G 3C 8G 0      ##STR85##      2 9G 9H 2C 5G 10E 0 2C 4H 1C 1C 1C 8G 1C 2G 9H 2G      ##STR86##      2 0 0 0 0 0 0 0 0 0 0 0 0      ##STR87##      2 0 0 0 0 0 0 0 0 0 0 0 0      ##STR88##      2 6H 2C 0 0 0 0 0 0 2C 2G 1C 5G 0

Test B

Two plastic bulb pans were filled with fertilized and limed Fallsingtonsilt loam soil. One pan was planted with corn, sorghum, Kentuckybluegrass and several grassy weeds. The other pan was planted withcotton, soybeans, purple nutsedge (Cyperus rotundus), and severalbroadleaf weeds. The following grassy and broadleaf weeds were planted:crabgrass (Digitaria sanguinalis), barnyardgrass (Echinochloacrusgalli), wild oats (Avena fatua), johnsongrass (Sorghum halepense),dallisgrass (Paspalum dilatatum), giant foxtail (Setaria faberii),cheatgrass (Bromus secalinus), mustard (Brassica arvensis), cocklebur(Xanthium pennsylvanicum), pigweed (Amaranthus retroflexus),morningglory (Ipomoea hederacea), cassia (Cassia tora), teaweed (Sidaspinosa), velvetleaf (Abutilon theophrasti), and jimsonweed (Daturastramonium). A 12.5 cm diameter plastic pot was also filled withprepared soil and planted with rice and wheat. Another 12.5 cm pot wasplanted with sugarbeets. The above four containers were treatedpre-emergence with several test compounds within the scope of theinvention.

Twenty-eight days after treatment, the plants were evaluated andvisually rated for response to the chemical treatments utilizing therating system described previously for Test A. The data are summarizedin Table XIX. Note that the compounds are useful as pre-emergencetreatments for weed control in crops such as soybeans.

                  TABLE XIX                                                       ______________________________________                                        SECONDARY PRE-EMERGENCE                                                       ON FALLSINGTON SILT LOAM                                                                      Rate, kg/ha                                                                   0.06      0.25                                                ______________________________________                                        Compound                                                                       ##STR89##                                                                    Crabgrass         7G          10C                                             Barnyardgrass     9G,9C       10C                                             Sorghum           10C         10E                                             Wild Oats         0           4G                                              Johnsongrass      9G,9C       10C                                             Dallisgrass       5G          7G                                              Giant Foxtail     10C         10C                                             Ky. Bluegrass     10E         10E                                             Cheatgrass        8G,9C       10C                                             Sugarbeets        10C         10C                                             Corn              10C         10E                                             Mustard           10C         10C                                             Cocklebur         8G,5H       8G,9H                                           Pigweed           10E         10E                                             Nutsedge          5G          7G                                              Cotton            8G          8G                                              Morningglory      8G,7C       10C                                             Cassia            8G,8C       8G,9C                                           Teaweed           10C         10C                                             Velvetleaf        8G,8C       10C                                             Jimsonweed        7G          8G,9C                                           Soybean           10E         10E                                             Rice              4G          7G,3C                                           Wheat                                                                         Compound                                                                       ##STR90##                                                                    Crabgrass         9G,6C       10C                                             Barnyardgrass     10C         10C                                             Sorghum           10C         10E                                             Wild Oats         7G,3C       10C                                             Johnsongrass      9G,9C       10C                                             Dallisgrass       9G,5C       10C                                             Giant Foxtail     10C         10C                                             Ky. Bluegrass     10E         10E                                             Cheatgrass        10E         10E                                             Sugarbeets        10C         10C                                             Corn              9G,8C       10E                                             Mustard           10C         10C                                             Cocklebur         8G,5H       8G,8H                                           Pigweed           10E         10E                                             Nutsedge          8G          10E                                             Cotton            8G          8G                                              Morningglory      8G,8C       8G,8C                                           Cassia            8G,8C       8G,8C                                           Teaweed           10C         10C                                             Velvetleaf        10C         10C                                             Jimsonweed        8G,8C       8G,9C                                           Soybean           8G,8C       8G,9C                                           Rice              10E         10E                                             Wheat             10C         10C                                             ______________________________________                                    

Test C

Two compounds,2-chloro-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl-3-pyridinesulfonamide,(Compound A) and2-chloro-N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl], (CompoundB), were applied pre- and post-emergence to a number of crops and weedsunder field conditions. The post-emergence treatment was applied 20 daysafter planting the crops. The following data show that one or the otherof the two compounds exhibits pre- and/or post-emergence selectivity oncucumber, squash, flax, wheat, oats and tomato.

                                      TABLE XX                                    __________________________________________________________________________    Rate,    % Control Overall                                                    Active   Grasses   Broadleaves                                                                             % Control - 5 weeks                              Materials                                                                          kg/ha                                                                             5 Weeks                                                                            11 Weeks                                                                           5 Weeks                                                                            11 Weeks                                                                           Flax                                                                             Tomato                                                                             Cucumber                                                                            Squash                                                                            Oats                                                                             Wheat                       __________________________________________________________________________    Pre-Emergence                                                                 Comp. A                                                                            .015                                                                              50    0   65   50    0 20    0    20   0  0                               .031                                                                              70   20   92   80    0 30   30    30   0  0                               .063                                                                              85   30   98   80   20 20   25    70  15 10                          Comp. B                                                                            .015                                                                              98   80   100  99    0 30    0    20  70 30                               .031                                                                              100  80   100  98   15 50   25    20  72 55                          Post-Emergence                                                                Comp. A                                                                            .015                                                                              80    50  90   50    0 80    0    70   0  0                               .031                                                                              85    90  94   70    0 80   30    95   0  0                               .063                                                                              98    98  98   95    0 98   70    95   0  0                          Comp. B                                                                            .015                                                                              92    95  98   40   30  0    0    55  60 20                               .031                                                                              98    98  98   75   40  0    0    40  70 50                               .063                                                                              99    99  99   90   60  0   30    60  90 70                          __________________________________________________________________________

What is claimed is:
 1. A compound of the formula: ##STR91## R₁ is H, Cl,Br, F, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, COOR₅, NR₆ R₇ orSO₂ NR₁₀ R₁₁ ;R₂ is H, Cl, Br or CH₃ ; R₃ and R₄ are independently H orCH₃ ; R₅ is C₁ -C₆ alkyl, C₃ -C₆ alkenyl, CH₂ CH₂ OCH₃, CH₂ CH₂ OCH₂CH₃, CH₂ CH₂ CH₂ OCH₃ or CH₂ CH₂ Cl; R₆ and R₇ are independently CH₃ orCH₃ CH₂ ; R₆ and R₇ can be taken together to form --(CH₂)₄ --, --(CH₂)₅-- or --CH₂ CH₂ OCH₂ CH₂ --; R₁₀ and R₁₁ are independently CH₃ or CH₃CH₂ ; W is oxygen or sulfur; X is CH₃, --OCH₃ or --OCH₂ CH₃ ; Y is H,Cl, CH₃, CF₃, --NHCH₃, --N(CH₃)₂ --, --CH₂ OR₈, --CH₂ CH₂ OR₈, --OCH₂CF₃ or VR₉ ; Z is CH; V is oxygen or sulfur; R₈ is CH₃ or CH₃ CH₂ ; orR₉ is CH₃, CH₃ CH₂, CH₂ CO₂ R₈, CH₂ CH₂ OR₈, C(CH₃)HCO₂ R₈ or CH₂ CH₂CO₂ R₈ ;and agricultural salts thereof; providing that: R₁ is at the 2-or 4-position of the pyridine ring.
 2. A compound of claim 1 wherein R₃is H and W is oxygen.
 3. A compound of claim 2 wherein R₂ is hydrogen.4. A compound of claim 3 wherein R₁ is Cl, CH₃ O or CH₃.
 5. Compounds ofclaim 4 wherein R₁ is 2- or 4-chloro.
 6. A compound of claim 5 whereinR₄ is hydrogen.
 7. A compound of claim 5 wherein R₁ is chlorine.
 8. Acompound of claim 5 wherein X is CH₃ or --OCH₃ ; and Y is CH₃, --OCH₃,OCH₂ CH₃ or --CH₂ OCH₃.
 9. A compound of claim 8 wherein R₃ and R₄ arehydrogen and W is oxygen.
 10. The compound of claim 1,2-chloro-N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl)]-3-pyridinesulfonamide.11. The compound of claim 1,2-chloro-N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-3-pyridinesulfonamide.12. The compound of claim 1,2-chloro-N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-3-pyridinesulfonamide.13. A composition suitable for controlling the growth of undesiredvegetation which comprises an effective amount of a compound of claim 1and at least one of the following: surfactant, solid or liquid diluent.14. A composition suitable for controlling the growth of undesiredvegetation which comprises an effective amount of a compound of claim 2and at least one of the following: surfactant, solid or liquid diluent.15. A composition suitable for controlling the growth of undesiredvegetation which comprises an effective amount of a compound of claim 3and at least one of the following: surfactant, solid or liquid diluent.16. A composition suitable for controlling the growth of undesiredvegetation which comprises an effective amount of a compound of claim 4and at least one of the following: surfactant, solid or liquid diluent.17. A composition suitable for controlling the growth of undesiredvegetation which comprises an effective amount of a compound of claim 5and at least one of the following: surfactant, solid or liquid diluent.18. A composition suitable for controlling the growth of undesiredvegetation which comprises an effective amount of a compound of claim 6and at least one of the following: surfactant, solid or liquid diluent.19. A composition suitable for controlling the growth of undesiredvegetation which comprises an effective amount of the compound of claim7 and at least one of the following: surfactant, solid or liquiddiluent.
 20. A method for controlling the growth of undesired vegetationwhich comprises applying to the locus to be protected an effectiveamount of a compound of claim
 1. 21. A method for controlling the growthof undesired vegetation which comprises applying to the locus to beprotected an effective amount of a compound of claim
 2. 22. A method forcontrolling the growth of undesired vegetation which comprises applyingto the locus to be protected an effective amount of a compound of claim3.
 23. A method for controlling the growth of undesired vegetation whichcomprises applying to the locus to be protected an effective amount of acompound of claim
 4. 24. A method for controlling the growth ofundesired vegetation which comprises applying to the locus to beprotected an effective amount of a compound of claim
 5. 25. A method forcontrolling the growth of undesired vegetation which comprises applyingto the locus to be protected an effective amount of a compound of claim6.
 26. A method for controlling the growth of undesired vegetation whichcomprises applying to the locus to be protected an effective amount ofthe compound of claim 7.